WO2005052012A1 - Resines hdpe de poids moleculaire eleve - Google Patents

Resines hdpe de poids moleculaire eleve Download PDF

Info

Publication number
WO2005052012A1
WO2005052012A1 PCT/US2003/034679 US0334679W WO2005052012A1 WO 2005052012 A1 WO2005052012 A1 WO 2005052012A1 US 0334679 W US0334679 W US 0334679W WO 2005052012 A1 WO2005052012 A1 WO 2005052012A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
temperature
catalyst
resin
astm
Prior art date
Application number
PCT/US2003/034679
Other languages
English (en)
Inventor
Scott T. Roger
Thomas W. Towles
Anthony N. Speca
Stanley J. Katzen
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to AU2003284383A priority Critical patent/AU2003284383A1/en
Priority to PCT/US2003/034679 priority patent/WO2005052012A1/fr
Priority to US10/973,805 priority patent/US20050119426A1/en
Priority to US11/058,814 priority patent/US7384885B2/en
Publication of WO2005052012A1 publication Critical patent/WO2005052012A1/fr

Links

Classifications

    • 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

Definitions

  • This invention is related to a method of producing a high molecular weight HDPE particularly suitable for blow molding and sheet extrusion/thermoforming applications, such as manufacture of large parts.
  • High molecular weight, high density polyethylene is used to manufacture storage containers, such as large industrial drums (e.g., 30- and 55- gallons) and intermediate bulk containers (IBC) such as 100- and 300-gallon containers.
  • HMW HDPE is also used in sheet extrusion/thermoforming operations to produce large parts such as truck bed liners, "port-a-potties” or portable toilets, and "dunnage trays” for holding and transporting large industrial parts such as transmissions.
  • the end user expects - and governmental regulations often require - that the container meet certain minimum requirements, such as for impact resistance, top load, Environmental Stress Crack Resistance (ESCR), and chemical resistance.
  • ESCR Environmental Stress Crack Resistance
  • chemical resistance the manufacturer of the containers expect ease of processability.
  • a chromium compound such as chromium oxide
  • a support of one or more inorganic oxides such as silica, alumina, zirconia or thoria
  • inorganic oxides such as silica, alumina, zirconia or thoria
  • U.S. Patent No. 2,825,721 describes chromium catalysts and methods of making the catalysts. It is also known to increase polymer melt index by using a silica-titania support as disclosed, for example, in U.S. Patent No. 3,887,494. Numerous activation procedures have been described in the prior art for optimizing catalyst performance and resultant ethylene polymer characteristics, such as U.S. Patent Nos.
  • Embodiments of the present invention may have the advantage over previously known methods of producing blow molding HDPE by having an improved ESCR versus density relationship, yet maintaining good processing and stiffness characteristics.
  • a process to polymerize ethylene, or ethylene and at least one other olef ⁇ n, particularly an alpha olefin, and even more particularly an alpha olefin comprising 3 to 10 carbon atoms to produce a polymer particularly suitable for the large part molding market, (e.g., blow molding, sheet extrusion/thermoforming especially in the production of containers such as 30- and 55-gallon drums and IBCs.
  • an object of the invention is to provide an activated catalyst for the manufacture of blow molding resin.
  • the invention provides polyethylene resins produced by the inventive process, and articles formed of such resins.
  • Typical articles include, for example, containers for the shipping of large industrial parts, and industrial bulk containers such as drums (e.g., 30- and 55-gallon drums), and the like, and 100-, 300-, and 400-gallon IBCs, and the like.
  • the support is a silica-titania support.
  • Silica-titania supports are well known in the art and are described, for example, in U.S. Patent No. 3,887,494.
  • Silica-titania supports can be produced as described in U.S. Patent Nos. 3,887,494, 5,096,868 or 6,174,981 by "cogelling" or coprecipitating silica and a titanium compound.
  • Such a cogel can be produced by contacting an alkali metal silicate such as sodium silicate with an acid such as sulfuric acid, hydrochloric acid or acetic acid, or an acidic salt.
  • the titanium component can be conveniently dissolved in the acid or alkali metal silicate solution and co- precipitated with the silica.
  • the titanium compound can be incorporated in the acid in any form in which it subsequently will be incorporated in the silica gel formed on combination of the silicate and the acid and from which form it is subsequently convertible to titanium oxide on calcination.
  • Suitable titanium compounds include, but are not limited to, halides such as TiCl 3 and TiCl 4 , nitrates, sulfates, oxalates and alkyl titanates. In instances where carbon dioxide is used as the acid, the titanium can be incorporated into the alkali metal silicate itself.
  • the titanium compound can be incorporated in the alkali metal silicate and in such instances, convenient titanium compounds are water soluble materials which do not precipitate the silicate, i.e., are those convertible to titanium oxide on calcination such as, for example, various titanium oxalates, such as K 2 TiO(C 2 0 4 ) 2 -H 2 O, (NH 4 ) 2 TiO(C 2 O 4 ) 2 -H 2 O and Ti 2 (C 2 O 4 ) 3 ⁇ 2 O.
  • various titanium oxalates such as K 2 TiO(C 2 0 4 ) 2 -H 2 O, (NH 4 ) 2 TiO(C 2 O 4 ) 2 -H 2 O and Ti 2 (C 2 O 4 ) 3 ⁇ 2 O.
  • the term "silica-titania" support includes supports formed by any of these coprecipitation or cogel processes, or other processes by which titania and silica are both incorporated into the support.
  • titanium is incorporated by surface-modifying a supported chromium catalyst.
  • a supported chromium catalyst is meant to include any supported chromium catalyst that is further modified to include titanium; see, e.g., C.E. Marsden, Plastics, Rubber and Composites Processing and Applications, 21 (1994), 193- 200.
  • the alkyl group R of the alkoxide can be a C 3 to C 8 linear or branched alkyl group; a particular example of a suitable titanium alkoxide is titanium tetraisopropoxide.
  • the titanium compound preferably is generally present in an amount of from a lower limit of 0.5% or 1% or 2° o by weight to an upper limit of 12% or 10% or 8% or 6% or 5% or 4% or 3% by " weight, with ranges from any lower limit to any upper limit being contemplated. It is preferred that the amount of titanium be in the range of 1.0 wt.% to 5.0 wt.%, more preferably 1.5 wt.% to 4.5 wt.% (3.0 ⁇ 1.5 wt.%). In an embodiment, the even more preferable range is 2.5 ⁇ 0.5 wt.%.
  • the chromium compound can be incorporated in any convenient method known in the art.
  • a chromium compound and optionally a titanium compound is dissolved in an acidic material or the silicate and thus coprecipitated with the silica.
  • a suitable chromium compound for this method is chromic sulfate.
  • Another method to incorporate a chromium compound into the catalyst system is to use a hydrocarbon solution of a chromium compound convertible to chromium oxide to impregnate the support after it is spray dried or azeotrope dried (i.e., a xerogel). Exemplary of such materials are t-butyl chromate, chromium acetylacetonate, and the like.
  • Suitable solvents include, but are not limited to, pentane, hexane, benzene, and the like.
  • an aqueous solution of a chromium compound simply can be physically mixed with the support.
  • Chromium can be present in the catalyst an amount from a lower limit of 0.1 or 0.5 or 0.8 or 1.0% by weight to an upper limit of 10% or 8% or 5% or 4% or 3% or 2% by weight, with ranges from any lower limit to any upper limit being contemplated.
  • the preferred amount of chromium is about 1.0 ⁇ 0.5 wt.%, particularly when the process utilizes the slurry loop platform, discussed more fully below.
  • inorganic oxides may optionally be present, such as thoria, zirconia, boron oxide, alumina, and the like, but in a preferred embodiment, with regard to inorganic oxides other than that of the silica support, only the oxides of chromium and titanium are present to the extent provided by ordinary purification techniques. In another embodiment, additional metals are permissible provided they do not materially affect the basic characteristics of the catalyst or the activation procedure according to the present invention.
  • the weight percent of the aforementioned metals are based on the weight of the support, e.g, silica in the preferred embodiment.
  • Catalysts as described above which are useful in the present invention are commercially available, such as The PQ Corporation, W.R. Grace and Company, and Ineos Silicas Americas, LLC.
  • the catalyst treated by the process according to the present invention comprises chromium and titanium on a support.
  • the catalyst used in the process according to the present invention will be a commercial supported catalyst that may have hydrocarbon residues deposited thereon.
  • a beneficial hydrocarbon treatment has been described previously and used in activating catalysts for producing utility conduit resin and extruded pipe resin, in PCT/US03/09871, PCT/US03/09869 and PCT/US03/09870, respectively. It is highly surprising that such treatment could be useful in producing resin for blow molding and sheet extrusion/thermoforming applications.
  • the chromium and titanium-based supported catalyst to be treated by the method described herein has hydrocarbon residues deposited thereon.
  • Hydrocarbon residues as used herein means any species or moiety containing hydrogen and carbon, which is present on the catalyst and/or support. Without limitation, such hydrocarbon residues may be present on the catalyst and/or support as a result of having been deposited during the manufacture of the catalyst or support, such as organic solvent residues or by the deposition of one or more of chromium, titanium, zirconium, aluminum, and boron on the support from an organic solution (e.g., chromium acetate), such as described in the previously mentioned U.S Patent No. 5,895,770. Hydrocarbon residues may also be present in supported catalysts comprising chromium and/or titanium made by gel processes such as in the cogel and tergel catalysts described previously.
  • chromium and titanium-based supported catalyst is intended to distinguish the catalyst according to the present invention from a “chromium-based catalyst” which does not contain titanium.
  • Chromium and titanium and optional species, if present, may have been deposited from solution and hydrocarbon residues are present at least in part as a result of this deposition process (e.g., hydrocarbon residues may be from the solvent or metal counter ion). Hydrocarbon residues may also be present as a result of the manufacture or processing of the support.
  • the chromium and titanium-based supported catalyst according to the present invention is then placed in an activating reactor to be treated by the process according to the present invention.
  • the invention may be practiced using any known method for bringing gases and solids into contact with each other, such as in a static bed or a fluidizing bed.
  • activating reactor is not intended to be limiting with respect to equipment design or configuration, and the terms "activator” and “activating reactor” are used interchangably herein for convenience.
  • the activating reactor will be a fluidized bed reactor.
  • the activating reactor may be heated by, for instance, internal activator reactor rods, by an external source of heat applied to the activating reactor walls, such as electrical heat or by heat of combustion, by provision for heating the gas entering the activating reactor via one or more gas inlet valves, or by a combination of such heating sources, all of which can be measured and controlled by means per se well known.
  • an external source of heat applied to the activating reactor walls such as electrical heat or by heat of combustion
  • provision for heating the gas entering the activating reactor via one or more gas inlet valves or by a combination of such heating sources, all of which can be measured and controlled by means per se well known.
  • activator temperature is typically measured at or very close to the catalyst bed and thus, as would be understood by one of skill in the art, “activator temperature” is taken as surrogate for the temperature of the catalyst.
  • the catalyst used in the process according to the present invention is a chromium and titanium-based supported catalyst activated in activator at about 370-540°C (700-1000°F), preferably 370-450°C (700-850°F), more preferably 370-425°C (700-800°F), still more preferably 370 to 400°C (700-750°F), under an inert atmosphere, followed by the introduction of an oxidant, preferably in the form of air, and controlling the reactor temperature so that the temperature of the catalyst activator does not exceed 510°C (950°F), preferably no higher than about 480°C (900°F), and yet still more preferably no higher than about 450°C (850°F), most preferably no higher than about 425°C (800°F).
  • the activator temperature is controlled by the rate of addition of oxygen and by the temperature of the gas entering the activator.
  • the present invention also includes a process for polymerizing ethylene including treating a chromium and titanium-containing supported catalyst at about 370-400°C (700-750°F) under an inert atmosphere which may be at least partially preheated to a temperature higher or lower than the activating reactor temperature, followed by the controlled introduction of an oxidant, preferably in the form of air, which has been preheated to a temperature no greater than about 400°C (750°F), most preferably by air which has been preheated to about 200°C (400°F) or less, while controlling the temperature spike so that the temperature of the catalyst activator does not exceed 510°C (950°F), preferably no higher than about 480°C (900°F), and yet still more preferably no higher than about 450°C (850°F), most preferably no higher than about 425 °C (800°F).
  • additional hold periods at temperatures lower than 370°C are contemplated.
  • the activator temperature is ramped up from room temperature to about 205°C ⁇ 25°C (400°F ⁇ 45 °F) at about 220°C/hr (400F/hr) and held at this temperature under a nitrogen atmosphere for a period of one minute to up to about 6 hours, or even more, followed by a temperature ramp up to a preselected temperature between about 370-540°C (700-1000°F), preferably 370-450°C (700-850°F), more preferably 370-425°C (700-800°F), still more preferably 370 to 400°C (700-750°F), at a rate of about 200°C/hr (350°F/hr), while still under an inert atmosphere.
  • This temperature and inert atmosphere is then held constant for a period of from one minute up to about 6 hours.
  • the nitrogen (or inert gas) treatment may occur to an even higher temperature, however (without wishing to be bound by theory) it is believed that above about 540°C (1000°F) the supported chromium and titanium catalyst may be converted partially or wholly into a form ("green batch") which is less amenable to a subsequent treatment with oxygen. A green batch may also be observed under conditions where the oxygen is present at a concentration of less than about 20% by volume, i.e., less oxygen than is normally present in air. Thus temperatures of above about 540°C should be avoided during the treatment under pure nitrogen or other inert gaseous treatment and during conditions where pure nitrogen is mixed with air.
  • Activation may then be completed by contacting the catalyst in the activating reactor with an oxidizing atmosphere, preferably an atmosphere consisting essentially of air.
  • an oxidizing atmosphere preferably an atmosphere consisting essentially of air.
  • the final activation hold temperature is a key to the blow molding resin according to the present invention.
  • a lower final hold temperature yields a polymer having a better ESCR but its activity will be too low for economical polymerization reactor operation, while a higher final hold temperature yields improved polymerization reactor performance but without adequate ESCR.
  • activator temperature is typically measured at or very close to the catalyst bed and thus, as would be understood by one of skill in the art, "activating reactor temperature” or “activator” is taken as surrogate for the temperature of the catalyst.
  • the thus-activated supported chromium and titanium-based catalyst is then preferably cooled to about 150-315°C (300-600°F), purged with nitrogen while cooling to room temperature and then used as desired.
  • the ethylene used in the polymerization process should be polymerization grade ethylene.
  • the other olef ⁇ ns that can be used are alpha-olefins having from 3 to 10 carbon atoms. Numerous acceptable alpha-olef ⁇ ns will be apparent to one of ordinary skill in the art in possession of the present disclosure.
  • the preferred olefins to be copolymerized are 1-butene, 1-hexene, and 1-octene.
  • the resin according to the invention can be polymerized using any known process in the art for producing HDPE, such as gas phase, solution or slurry polymerization conditions.
  • A- stirred polymerization reactor can be utilized for a batch or continuous process, or the reaction can be carried out continuously in a loop reactor.
  • the polymerization occurs in a slurry loop reactor under slurry polymerization conditions.
  • a slurry loop reactor under slurry polymerization conditions.
  • Loop reactors are known in the art, see, for example, U.S. Pat. Nos. 3,248,179; 4,424,341; 4,501,855; 4,613,484; 4,589,957; 4,737,280; 5,597,892; and 5,575,979; 6,204,344; 6,281,300; 6,319,997; and 6,380,325.
  • the resin of the invention is preferably produced in a slurry reactor, such as a stirred slurry reactor or a slurry loop reactor.
  • a slurry reactor such as a stirred slurry reactor or a slurry loop reactor.
  • the methods are described below with particular reference to a slurry loop reactor. However, it should be appreciated that the methods are not limited to this particular polymerization reactor configuration.
  • a slurry loop olefin polymerization reactor can generally be described as a loop-shaped continuous pipe.
  • One or more fluid circulating devices such as an axial flow pump, circulate the reactor contents within the pipe in a desired direction so as to create a circulating current or flow of the reactor contents within the pipe.
  • the fluid circulating devices are designed to provide high velocity.
  • the loop reactor may be totally or partially jacketed with cooling water in order to remove heat generated by polymerization.
  • the polymerization medium includes monomer, optional comonomer and minor quantities of other additives, as known in the art, and a hydrocarbon carrier or diluent, advantageously aliphatic paraffin such as propane, butane, isobutane, isopentane, or mixtures thereof.
  • a hydrocarbon carrier or diluent advantageously aliphatic paraffin such as propane, butane, isobutane, isopentane, or mixtures thereof.
  • propane, butane, isobutane, isopentane or mixtures thereof.
  • the slurry loop olefin polymerization reactor may be operated in a single stage process or in multistage processes. In multistage processing, the polymerization of olefins is carried out in two or more polymerization reactors. These polymerization reactors can be configured in series, in parallel, or a combination thereof.
  • U.S. Pat. No. 6,380,325 sets forth a two stage flash process which is a preferred platform to practice the present invention.
  • the resin according to the present invention may be produced using the catalyst treated according to the processes described above by slurry loop polymerization conducted at temperature conditions in the range of about 88- 110°C (190-230°F).
  • a blow molding resin is produced preferably having a density of about 0.944-0.958 g/cm 3 , more preferably 0.950- 0.957 g/cm 3 (ASTM D-1505) and a preferred range of I 22 of about 2-12 g/10 min, more preferably 3-8 g/10 min (ASTM D-1238-65T, Condition F). These characteristics may be readily achieved by one of ordinary skill in the art in possession of the present disclosure.
  • HMW HDPE will have a weight average molecular weight ranging from about 100,000 g/mole to about 4,000,000 g/mole.
  • HDPE is typically defined as having a density above about .940 g/cm 3 .
  • the catalyst is placed in a fluidizing bed activating reactor of the type well-known in the art.
  • the activating reactor comprises heating rods to heat the catalyst bed and gas inlets with preheaters.
  • the catalyst is fluidized with dry N 2 and the temperature of the activating reactor/catalyst bed is ramped up at about 222°C/hr (400°F/hr) to 205°C (400°F). It is held at this temperature under a nitrogen flow of about 126 CFM (cubic feet per minute) for 4 hours and then ramped at about 195°C/hr (350°F/hr) to a hold at about 400°C (750°F) under a nitrogen flow of about 144 CFM.
  • the catalyst is held in the activating reactor under these conditions for about 3.5 hours.
  • the gas inlet preheaters are set to 450°C (850°F) during the period that the activating reactor temperature is held at 400°C (750°F) under nitrogen, and shortly before the introduction of the 20 CFM of air, the gas inlet preheaters are lowered to about 200°C (400°F).
  • a controlled amount of oxidant is introduced, in the form of dry air at a rate of 20 CFM, with a decrease in the nitrogen flow to approximately 122 CFM, so that the amount of oxygen in the activating reactor is at a concentration of about 2.8% by volume, while maintaining the activating reactor at about 400°C (750°F).
  • a temperature spike to about 425°C (800°F) is observed in the reactor shortly after the partial oxygen environment is introduced, but the activating reactor temperature approaches 400°C (750°F) within about 90 minutes.
  • the gas inlet preheaters remain set at about 200°C (400°F) during this period.
  • the atmosphere is then switched to 100% dry air and the temperature is ramped using both the activating reactor probe heaters and the gas inlet preheaters, at about 83°C (150°F/hr) to a 6 hour hold at 590°C (1100°F) and held for 6 hours, to complete activation.
  • the catalyst is then cooled to about 150-205°C (300-400°F) under an atmosphere of air and then fluidized with nitrogen and allowed to come to room temperature.
  • the thus-activated catalyst is used in a slurry loop polymerization process to produce HMW HDPE resin under the conditions previously described, using in this case 1-hexene as the comonomer.
  • the resin has a nominal I value (which may be referred to as Flow Rate 190/21.6 or HLMI) of 5.8 g/10 min (ASTM D-1238-65T, Condition F), a nominal density of 0.954 g/cm 3 (ASTM D-1505). These values are not intended to be performance specifications but represent typical values.
  • This resin is particularly suitable for 30- and 55-gallon drums, IBCs, and other large parts made by blow molding and/or sheet extrusion/thermoforming operations.
  • a process for producing a resin suitable for sheet extrusion/thermoforming and/or blow molding comprising polymerizing ethylene or ethylene and an alpha- olefin comonomer comprising 3 to 10 carbon atoms, in the presence of a chromium and titanium-based catalyst activated by: (i) contacting said catalyst in a activating reactor at a temperature of between about 370-540°C (700-1000°F) with an atmosphere consisting essentially of an inert gas; and then (ii)introducing an oxidant into said activating reactor so that the temperature of said activating reactor does not exceed about 510°C (950°F); and then (iii) completing the activation of said catalyst in a activating reactor at a temperature of about 548- 638°C (1020-1180°F) under an oxidizing atmosphere; and

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention concerne une résine polyéthylène convenant particulièrement aux pièces de grande taille produites selon des procédés de moulage par soufflage et/ou d'extrusion/thermoformage de feuilles, laquelle résine est fabriquée selon un procédé faisant appel à un catalyseur activé à base de titane et de chrome.
PCT/US2003/034679 2003-03-31 2003-10-31 Resines hdpe de poids moleculaire eleve WO2005052012A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU2003284383A AU2003284383A1 (en) 2003-10-31 2003-10-31 High molecular weight hdpe resins
PCT/US2003/034679 WO2005052012A1 (fr) 2003-10-31 2003-10-31 Resines hdpe de poids moleculaire eleve
US10/973,805 US20050119426A1 (en) 2003-10-31 2004-10-25 High molecular weight HDPE resins
US11/058,814 US7384885B2 (en) 2003-03-31 2005-02-16 Catalyst activation and resins therefrom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2003/034679 WO2005052012A1 (fr) 2003-10-31 2003-10-31 Resines hdpe de poids moleculaire eleve

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/058,814 Continuation-In-Part US7384885B2 (en) 2003-03-31 2005-02-16 Catalyst activation and resins therefrom

Publications (1)

Publication Number Publication Date
WO2005052012A1 true WO2005052012A1 (fr) 2005-06-09

Family

ID=34632383

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/034679 WO2005052012A1 (fr) 2003-03-31 2003-10-31 Resines hdpe de poids moleculaire eleve

Country Status (2)

Country Link
AU (1) AU2003284383A1 (fr)
WO (1) WO2005052012A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006088602A2 (fr) * 2005-02-16 2006-08-24 Exxonmobil Chemical Patents, Inc. Resine pour tuyau extrude
US8372771B2 (en) 2010-02-16 2013-02-12 Chevrton Phillips Chemical Company LP System and method for catalyst activation
EP1907430B2 (fr) † 2005-07-27 2023-06-28 Univation Technologies, LLC Moulage par extrusion-soufflage de résines de polyéthylène

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172618A2 (fr) * 1984-07-13 1986-02-26 Kelman, Charles D. Lentille intra-oculaire
EP0364635A1 (fr) * 1987-05-28 1990-04-25 Mobil Oil Corporation Composition de catalyseur contenant du chrome modifié pour la polymérisation d'oléfines
EP0435515A1 (fr) * 1989-12-29 1991-07-03 BP Chemicals Limited Procédé de (co-)polymérisation de l'éthylène en phase gazeuse
US5096868A (en) * 1987-10-21 1992-03-17 Mobil Oil Corporation Catalyst composition for polymerizing alpha-olefins and alpha-olefins polymerization therewith
EP0882743A1 (fr) * 1997-06-06 1998-12-09 Fina Research S.A. Catalyseurs à base de chrome modifiés par titanation pour la production de polyéthlylène
US6174981B1 (en) * 1998-12-17 2001-01-16 Phillips Petroleum Company Polymerization process
US6201077B1 (en) * 1998-12-01 2001-03-13 Phillips Petroleum Company Process that produces polymers
US6204346B1 (en) * 1998-12-17 2001-03-20 Phillips Petroleum Co. Polymerization process
US6214947B1 (en) * 1997-06-06 2001-04-10 Fina Research, S.A. Production of polyethylene for blow moulding
US6372867B1 (en) * 1997-09-11 2002-04-16 Bp Chemical Limited Process for the gas phase polymerization of olefins

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172618A2 (fr) * 1984-07-13 1986-02-26 Kelman, Charles D. Lentille intra-oculaire
EP0364635A1 (fr) * 1987-05-28 1990-04-25 Mobil Oil Corporation Composition de catalyseur contenant du chrome modifié pour la polymérisation d'oléfines
US5096868A (en) * 1987-10-21 1992-03-17 Mobil Oil Corporation Catalyst composition for polymerizing alpha-olefins and alpha-olefins polymerization therewith
EP0435515A1 (fr) * 1989-12-29 1991-07-03 BP Chemicals Limited Procédé de (co-)polymérisation de l'éthylène en phase gazeuse
EP0882743A1 (fr) * 1997-06-06 1998-12-09 Fina Research S.A. Catalyseurs à base de chrome modifiés par titanation pour la production de polyéthlylène
US6214947B1 (en) * 1997-06-06 2001-04-10 Fina Research, S.A. Production of polyethylene for blow moulding
US6372867B1 (en) * 1997-09-11 2002-04-16 Bp Chemical Limited Process for the gas phase polymerization of olefins
US6201077B1 (en) * 1998-12-01 2001-03-13 Phillips Petroleum Company Process that produces polymers
US6174981B1 (en) * 1998-12-17 2001-01-16 Phillips Petroleum Company Polymerization process
US6204346B1 (en) * 1998-12-17 2001-03-20 Phillips Petroleum Co. Polymerization process

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7384885B2 (en) 2003-03-31 2008-06-10 Exxonmobil Chemical Patents Inc. Catalyst activation and resins therefrom
WO2006088602A2 (fr) * 2005-02-16 2006-08-24 Exxonmobil Chemical Patents, Inc. Resine pour tuyau extrude
WO2006088602A3 (fr) * 2005-02-16 2007-04-05 Exxonmobil Chem Patents Inc Resine pour tuyau extrude
US7691955B2 (en) 2005-02-16 2010-04-06 Exxonmobil Chemical Patents Inc. Catalyst activation and resins therefrom
EP1907430B2 (fr) † 2005-07-27 2023-06-28 Univation Technologies, LLC Moulage par extrusion-soufflage de résines de polyéthylène
US8372771B2 (en) 2010-02-16 2013-02-12 Chevrton Phillips Chemical Company LP System and method for catalyst activation

Also Published As

Publication number Publication date
AU2003284383A1 (en) 2005-06-17

Similar Documents

Publication Publication Date Title
US7384885B2 (en) Catalyst activation and resins therefrom
EP2205350B1 (fr) Procédés de préparation d'un catalyseur de polymérisation
JP5283129B2 (ja) クロム−ベースの触媒
JP5821746B2 (ja) エチレン系重合体の製造方法及びそれから得られたエチレン系重合体
KR20100109909A (ko) 신속하게 활성화되는 촉매
AU2011202295B2 (en) Chromium based polymerization catalyst, the method to prepare it and polymers prepared therewith
US7214642B2 (en) Methods of preparing active chromium/alumina catalysts via treatment with sulfate
MX2011009005A (es) Pelicula de polietileno que tiene propiedades de barrera mejoradas y metodos para su elaboracion.
EP2374537A2 (fr) Procédés de préparation de catalyseurs actifs de chrome/alumine via le traitement avec une sulfate et polymères produits à l'aide de catalyseurs de chrome/alumine
US7112643B2 (en) Polymers having low levels of long chain branching and methods of making the same
US20050119426A1 (en) High molecular weight HDPE resins
JP5175802B2 (ja) クロム系触媒を用いたエチレン系重合体の製造方法
EP2970527B1 (fr) Procédés de préparation d'un catalyseur de polymérisation
ES2442273T3 (es) Métodos para la preparación de un catalizador de polimerización
US4816432A (en) Catalyst composition for polymerizing alpha olefins
WO2005052012A1 (fr) Resines hdpe de poids moleculaire eleve
WO2014154784A1 (fr) Procédé de polymérisation pour la production de polyéthylène haute densité
JP5581305B2 (ja) エチレン重合用触媒、それを用いたポリエチレンの製造方法、並びにブロー成形製品用ポリエチレン及び大型ブロー成形製品用ポリエチレン
JP4653881B2 (ja) エチレン系重合体及びその製造方法
CN108203483B (zh) 一种聚乙烯的制备方法
JP5803774B2 (ja) エチレン重合用クロム触媒の製造方法
AU2012201734B2 (en) Chromium based polymerization catalyst, the method to prepare it and polymers prepared therewith
JP2008150566A (ja) エチレン系重合体の製造方法
JP2003313239A (ja) 大型中空成形体用ポリエチレン樹脂及び大型中空成形体

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 11058814

Country of ref document: US

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP