+

WO1995011263A1 - Catalyseur de polymerisation ou de copolymerisation d'olefines - Google Patents

Catalyseur de polymerisation ou de copolymerisation d'olefines

Info

Publication number
WO1995011263A1
WO1995011263A1 PCT/US1994/007232 US9407232W WO9511263A1 WO 1995011263 A1 WO1995011263 A1 WO 1995011263A1 US 9407232 W US9407232 W US 9407232W WO 9511263 A1 WO9511263 A1 WO 9511263A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
silica
catalyst
cyclopentadienyl
metallocene
Prior art date
Application number
PCT/US1994/007232
Other languages
English (en)
Inventor
Frederick Yip-Kwai Lo
Ann Lorette Pruden
Original Assignee
Mobil Oil Corporation
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 Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to CA002170883A priority Critical patent/CA2170883C/fr
Priority to KR1019960701986A priority patent/KR960704941A/ko
Priority to AU73179/94A priority patent/AU697757B2/en
Priority to EP94923257A priority patent/EP0724603A4/fr
Priority to JP7511749A priority patent/JPH09504563A/ja
Publication of WO1995011263A1 publication Critical patent/WO1995011263A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • This invention relates an olefin polymerization or copolymerization catalyst; it also relates to a method for making such a catalyst.
  • This sort of catalyst comprises metallocenes of transition metals, and is characterized by extremely high activity.
  • the catalyst of the invention operates smoothly in both the gas phase, e.g. fluid bed, and in slurry polymerizations.
  • the catalyst can produce high molecular weight polymer at temperature and pressure conditions typically found in a commercial fluid bed reactor.
  • the catalyst can yield high bulk density, granular linear low density polyethylene in slurry polymerizations without reactor fouling.
  • the polymer products generally 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 the original processes exhibited medium-to-broad molecular weight distribution.
  • the catalyst To be commercially useful in the gas phase fluid bed process, or slurry reactor process, undertaken at low pressures less than about 1000 psi (6.89 MPa) , the catalyst must exhibit high activity, with concomittant 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 m MA n B p . These compounds in combination with methylalumoxane (MAO) have been used to produce olefin polymers and copolymers, such as ethylene and propylene homopolymers, ethylene-butene and ethylene-hexene copolymers, e.g., see US-A-4542199 and US-A-4404344.
  • Aluminoxanes e.g. methylalumoxane (MAO)
  • MAO metallocene catalysts
  • the class of alumoxanes comprises oligomeric linear and/or cyclic alkylalumoxanes represented by the formula:
  • n is 1-40, preferably 10-20, is 3-40, preferably 3-20 and R is a C 1 -C 8 alkyl group and preferably methyl.
  • Methylalumoxane is commonly produced by reacting trimethylaluminum with water or with hydrated inorganic salts, such as CuS0 4 .5H 2 0 or Al 2 (S0 4 ) 3 .5H 2 0. 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 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 resulting non-homogeneous polymerization gives low catalyst activity and poor product properties.
  • the invention relates to a metallocene catalyst which does not require an aluminoxane co-feed 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, which comprises particles of silica, a transition metal and aluminum, wherein:
  • silica is amorphous, porous, has a pore volume of 0.1 to 5 cm3/g and has a concentration of silanol groups wherein the concentration of silanol groups is at least 0.7 mmole per gram of silica;
  • transition metal and said aluminum being provided by a mixture of a metallocene and an alumoxane
  • the catalyst of the invention comprise a silica carrier, an alumoxane and at least one metallocene.
  • the catalyst is particulate in form, preferably comprising dry, free-flowing, powder particles having a particle size of from 1 to 500 microns, more preferably 1 to 250 microns, and most preferably from 10 to 150 microns.
  • the catalyst which preferably contains only one transition metal in the form of the metallocene has an activity of at least about 200 kg polymer/g of transition metals.
  • the aluminoxane and metallocene loading on the carrier is preferably such that the amount of aluminum, (elemental basis) provided by the aluminoxane, on the carrier ranges from 1 to 40 weight percent, preferably from 5 to 30 weight percent, and most preferably from 5 to 15 weight percent.
  • 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 transferring the catalyst.
  • the amount of metallocene on the carrier preferably ranges from 0.001 to 10 weight percent, more preferably from 0.5 to 0.3, and most preferably from 0.05 to 0.2 weight percent. Accordingly the ratio of Al:Zr (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 about 70 to 350 or 100 to 350, and most preferably from 100 to 200.
  • the carrier material is preferably solid and particulate.
  • the carrier is silica in the form of spherical particles, e.g., as obtained by a spray-drying process.
  • the carrier material is preferably used in the form of a dry powder having an particle size of from 1 to 500 microns, more preferably from 1 to 250 microns, and most preferably from 10 microns to 150 microns particle size.
  • the final catalyst containing carrier material may be sieved to insure elimination of large catalyst particles.
  • elimination of 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, 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 preferably is at least about 3 m 2 /g, more preferably, 5 to 1200 m 2 /g and most preferably at least about 50 m 2 /g up to about 350 m 2 /g.
  • the pore volume of the carrier will range from 0.1 to 5 cm 3 /g, preferably from 0.1 to 3.5 cm 3 /g.
  • the carrier material should preferably be dry, that is, free of absorbed water.
  • the carrier material must have at least some active hydroxyl (OH) groups to produce the catalyst composition of this invention.
  • the hydroxyl group concentration must be at least about 0.7 mmole/gram silica.
  • the hydroxyl group concentration is greater than 0.7 mmole/gram silica; more preferably it is at least 0.75 mmole/gram silica; and still more preferably it is at least 0.8 mmole/gram silica.
  • the preferred upper limit for the hydroxyl group concentration is 2.5 mmoles/gram silica.
  • the hydroxyl group concentration of the silica ranges from 1.6 to 2.5 mmoles/gram silica. This range is favored by lower drying, dehydration and/or calcination temperatures.
  • the most preferred range is 1.6 to 1.9 mmoles hydroxyl groups/gram silica.
  • the silica hydroxyl (herein silanol, silica hydroxyl is used interchangeably) groups are detectable by IR spectroscopy. Quantitative determinations of the hydroxyl concentration on silica are made by contacting a silica sample with methyl magnesium * iodide and measuring methane evolution (by pressure determination) .
  • Dehydration of silica material can be effected by heating at 100°C to 600°C, preferably from 150°C to 300°C and most preferably at 250°C.
  • silica dehydrated at 600°C will have a surface hydroxyl concentration of about 0.7 mmoles per gram (mmols/g) of silica.
  • Silica dehydrated at 800°C will be a silica with 0.5 mmole of silica hydroxy per gram silica.
  • the effect of silica hydroxyl groups on the catalyst activity and productivity is reflected in the EXAMPLES below.
  • 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.
  • scavengers such as trialkylaluminum compounds, e.g., trimethylaluminum (TMA)
  • Silicas containing higher hydroxyl numbers produce catalysts of higher activity than silicas of lower hydroxyl numbers; US patent application No 08/141912 it was shown that treating the silica with trimethylaluminum to react with the silanol [which, with appropriate molar amount of TMA the hydroxyl concentration is reduced to 0 (zero) , as indicated by IR (infrared) ] prior to catalyst synthesis produced a catalyst with a productivity of about 200 kg(polymer)/g (transition metal. By comparison, the catalysts produce herein with a hydroxyl group content of 1.8 mmole/gram silica exhibits a productivity of about 1000 kg(polymer)/g transition metal.
  • 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 about 600°C reduce the amount of reactive hydroxyl groups available for contact with the solution of aluminoxane and metallocene. By comparison, the dehydration temperatures of about 250°C increase the amount of reactive hydroxyl groups available for contact with the solution of aluminoxane and metallocene, relative to the silica heat treated, for dehydration purposes to 600°C. Thus it has been found that the catalyst made with the silica subjected to dehydration temperatures of 250°C is more active than a catalyst produced with the silica subjected to drying temperatures of 600°C. Accordingly, preferred dehydration and/or calcination temperatures are below 400°C, more preferably below 300°C, and most preferably at about 250°C.
  • all catalyst components can be dissolved with alumoxane and impregnated into the carrier.
  • Catalyst preparation is preferably undertaken under anhydrous conditions and in the absence of oxygen.
  • the carrier material can be impregnated with alumoxane, preferably methylalumoxane, in a process described below.
  • alumoxane preferably methylalumoxane
  • the class of alumoxanes comprises oligomeric linear and/or cyclic alkylalumoxanes represented by one of the formulae:
  • n is 1-40, preferably 10-20, is 3-40, preferably 3-20 and R is a C 1 -C 8 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 about 1200. MAO is typically kept in solution in toluene.
  • the volume of the solution comprising an alumoxane and a solvent therefor can vary, depending on the catalyst sought to be produced.
  • one of the controlling factors in the alumoxane incorporation into the carrier material catalyst synthesis is the pore volume of the silica.
  • the process of impregnating the carrier material is by infusion of the alumoxane solution, without forming a slurry of the carrier material, such as silica, in the alumoxane solution. This is undertaken with agitation.
  • the volume of the solution of the alumoxane is sufficient to fill the pores of the carrier material without forming a slurry in which the volume of the solution exceeds the pore volume of the silica; accordingly, the maximum volume of the alumoxane solution does not exceed the total pore volume of the carrier material. That maximum volume of the alumoxane solution ensures that no slurry of silica in solvent is formed in this step.
  • the pore volume of the carrier material is 1.65 cm 3 /g
  • the volume of alumoxane will be equal to or less than 1.65 cm 3 /g 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., cm 3 /g, times the total weight of the carrier used.
  • the impregnated carrier material will appear dry immediately following impregnation although the pores of the carrier may be filled with inter alia solvent.
  • the solution volume can be up to 30% greater than the total pore volume of the silica with the result(s) that no slurry of the silica is formed and that the silica remains dry in appearance.
  • the preferred solvent for the aluminoxane e.g. methaluminoxane, is toluene. The advantage is that the impregnation is undertaken in a single solvent system.
  • Solvent may be removed from the alumoxane impregnated pores of the carrier material by heating and/or under a vacuum or purged with heating in an inert gas, such as nitrogen. If 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 about 40°C and below about 50°C to obviate agglomeration of catalyst particles and crosslinking of the alumoxane. Preferably 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 maximum volume of the alumoxane solution also containing the metallocene is the total pore volume of the carrier material sample.
  • the mole ratio of aluminum provided by aluminoxane, expressed as Al, to metallocene metal expressed as M (e.g. Zr) preferably ranges from 50 to 500, more preferably 75 to 300, and most preferably 100 to 200.
  • An added advantage of the present invention is that this Al:Zr ratio can be directly controlled.
  • the alumoxane and metallocene compound are mixed together at ambient temperature for 0.1 to 6.0 hours, prior to use in the infusion step.
  • the solvent for the metallocene and alumoxane can be appropriate solvents, such as aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, cyclic ethers or esters; preferably it is toluene.
  • the metallocene compound has the formula Cp m MA n B 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 cyclopentadienyl group.
  • the substituents on the cyclopentadienyl group can be preferably straight-or branched chain c ⁇ c 6 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 n -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 n -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.
  • substituents A and B in the above formula of the metallocene compound are alkyl groups, they are preferably straight-chain or branched C j -C 8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl or n-octyl.
  • Suitable metallocene compounds include bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and bis(indenyl)metal dihalides wherein the metal is zirconium or hafnium, halide groups are preferably chlorine and the alkyl groups are C ⁇ C g alkyls.
  • metallocenes include bis(cyclopentadienyl)zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl , bis ( cyclopentadienyl ) haf nium 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- butylcyclopentadieny 1 ) hafnium dimethyl, bis(n- butylcycl ⁇ pentadienyl) zir
  • These catalysts are effective to form uniform blocks of alpha olefins of 3 to 10 carbon atoms, in a polymer containing a predominant amount of polymerized ethylene. These catalysts are unique in that they do form uniform blocks of alpha olefins of 3 to 10 carbon atoms, in a polymer containing a predominant amount of polymerized ethylene, in processes run at low pressures, up to, specifically no greater than, 400 psi (2.8 MPa) , at temperatures up to 130°C.
  • 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 practical 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 (2.8 MPa), such as solution and high pressure slurry polymerizations.
  • an operating temperature of about 30°C to 115°C is preferred, and a temperature of about 70°C to 106°C is most preferred.
  • Temperatures of about 75°C to 90°C are used to prepare products having a density of about 0.91 to 0.92, and temperatures of about 80°C to 100°C are used to prepare products having a density of about 0.92 to 0.94, and temperatures of about 90°C to 115°C are used to prepare products having a density of about 0.94 to 0.96.
  • linear low density production is conducted at about 85°C and high density product is formed at about 105°C.
  • slurry polymerization linear low density production is conducted at about 70°C and high density production is conducted at about 90°C.
  • pressures are below 10000 psi (69 MPa), preferably below 1000 psi (6.9 MPa).
  • the fluid bed reactor is operated at pressures of up to about 1000 psi (6.9 MPa), and is preferably operated at a pressure of from about 150 to 350 psi (1.0 to 2.4 MPa), with operation at the higher pressures in such ranges favouring 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 present 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. Instead, 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. Since the rate of heat generation is directly related to product formation, a measurement of the temperature rise of the gas across the reactor (the difference between inlet gas temperature and exit gas temperature) is determinative of the rate of particulate polymer formation at a constant gas velocity.
  • FIG. 1 A fluidized bed reaction system which can be used in the practice of the process of the present invention is shown in Fig. 1.
  • the reactor 10 consists of a reaction zone 12, a velocity reduction zone 14 and the distributor plate 20.
  • fouling can occur in all of the cold areas (areas in a reactor at a temperature which is less than the temperature at which any components, in the gas phase reactor is liquid rather than gaseous) distributor plate fouling is the one most easily detected, since it results in a rapid increase in the pressure drop across the distributor plate due to flow restriction. Such flow restrictions also result in changing fluidization patterns and contribute to reactor wall fouling.
  • the lowest temperature in the reactor loop is in the reactor inlet beneath the distributor plate.
  • Other areas representing the coldest sections in the fluid bed reactor system include the cooler and piping between the cooler and the bottom head.
  • the reaction zone 12 comprises a bed of growing polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of polymerizable and modifying gaseous components.
  • the mass gas flow rate through the bed must be above the minimum flow required for fluidization, and preferably from about 1.5 to about 10 times Gmf and more preferably from about 3 to about 6 times Gmf.
  • Gmf is used in the accepted form as the abbreviation for the minimum mass gas flow required to achieve fluidization (see C. Y. Wen and Y. H. Yu, "Mechanics of Fluidization", Chemical Engineering Progress Symposium Series. Vol. 62, p. 100- 111 (1966)).
  • the distribution plate 20 serves the purpose of diffusing recycle gas through the bed at a rate sufficient to maintain fluidization at the base of the bed. Fluidization is achieved by a high rate of gas recycle to and through the bed, typically in the order of about 50 times the rate of feed of make-up gas. Make-up gas is fed to the bed at a rate equal to the rate at which particulate polymer product is formed by reaction. The composition of the make-up gas is determined by a gas analyzer 16 positioned above the bed. The composition of the make-up gas is continuously adjusted to maintain an essentially steady state gaseous composition within the reaction zone.
  • the portion of the gas stream which does not react in the bed passes a velocity reduction zone 14 where entrained particles are given an opportunity to drop back into the bed, through a cyclone 22, through a filter 24 (optionally) and is compressed in a compressor 25, passes through a heat exchanger 26 and is returned to the bed.
  • the distribution plate 20 serves the purpose of diffusing recycle gas through the bed at a rate sufficient to maintain fluidization.
  • the plate may be a screen, slotted plate, perforated plate, a plate of the bubble cap type, and the like.
  • the elements of the plate may all be stationary, or the plate may be of the mobile type disclosed in US-A-3298792.
  • the fluidized bed is maintained at essentially a constant height by withdrawing a portion of the bed as product at a rate equal to the rate of formation of the particulate polymer product.
  • Both low density (0.91 to 0.939 g/cm 3 ) and high density (0.94 to 0.965 g/cm 3 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 40 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-olefins, 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 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/1-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 percent 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 about 0 to about 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°C to 120°C, depending on comonomer composition.
  • the catalyst of the invention contains only one source of transition metal, the 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 (0.38 to 0.89 mm), settled bulk density from 25 to 36 lb/ft 3 (400 to 577 kg/m 3 ) .
  • the particles of product are spherical.
  • the narrow molecular weight distribution low density copolymers have been produced with MI of between 1 and 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 121/12 [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] .
  • MFR melt flow ratio
  • 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.
  • MAO methaluminoxane
  • WITCO previously Schering Berlin
  • Polymerization was conducted in a 2 liter slurry reactor.
  • One liter polymerization grade heptane, 100 cm 3 1-hexene, and 2 cm 3 tri-isobutyl aluminum (TIBA, 25 wt% in heptane) were added to the reactor at room temperature.
  • the reactor contents were then agitated at 900 rpm and heated up to 70°C.
  • Ethylene was then added to maintain a constant pressure of 125 psig (0.86 MPa) in the reactor.
  • About 80 to 120 mg of a catalyst from the examples was injected into the reactor. Results are shown in Table 1, 2 and 3 (located at the end of the description) .
  • Catalyst (A) is the most active catalyst.
  • Catalyst (A) uses a Davison 955 silica dehydrated at 250°C and therefore has the most reactive surface with 1.8 mmole hydroxyl group per gram of silica.
  • Catalyst (B) is the second most active using Davison 955 silica dehydrated at 600°C with 0.72 mmole of hydroxyl group per gram of silica.
  • the reaction between themetallocene/methylaluminoxane solutionwith hydroxyl groups on the silica surface is a very important step in producing a highly active catalyst.
  • Catalyst (C) , (D) , and (E) are examples that use either Davison 955 (for catalyst (C) ) or PQ 988 silica (for catalyst (D) and (E) ) .
  • the silicas were dehydrated at 600°C and then treated with trimethylaluminum to remove all the hydroxyl group on the silica surface. Without the reactive hydroxyl groups on the surface, all three of these catalysts showed poorer activity.
  • catalyst (E) was prepared using additional toluene (2500 cm 3 ) to slurry the silica before drying at 60°C for 24 hours. This example illustrates that excess solvent during the preparation step and long drying time at higher temperature (60°C rather than 45°C) produce a very poor catalyst.
  • Table 2 shows that wide ranges of loadings of methylaluminoxane and metallocene can be used to react with Davison 955 silica dehydrated at 600°C.
  • the loadings are summarized below: Per gram silica Al/Zr mmole Al mmole Zr mole ratio
  • Catalyst (J) shows that multiple-step dry- impregnation (incipient wetness method) of the catalyst also produces a high activity catalyst.
  • Table 3 shows an example where bis(tetrahydroindenyl) zirconium dichloride can be used instead of bis(n- butylcyclopentadienyl) zirconium dichloride.
  • Other metallocene compounds can also be used.
  • a two-liter stainless steel autoclave was fitted with an anchor-type agitator. It was cleaned and purged with nitrogen at 100°C to remove air and moisture. 20 gram of 955-600 silica, treated with 2 cm 3 of trimethylaluminum (TMA, 15 wt% in heptane) were blended with 40 to 150 mg of a catalyst under nitrogen. The entire content was charged into the autoclave under nitrogen. 10 cm 3 of heptane and 5 cm 3 of hexene were injected into the reactor. The reactor temperature was set at 80°C and the reactor pressure was maintained at 175 psig (1.20 MPa) by a continuous supply of ethylene. Small portions of hexene were injected into the reactor at regular intervals to replenish the amount consumed.
  • TMA trimethylaluminum
  • the resin settled bulk density in all cases is between 28 to 34 lb/ft 3 (450 to 546 kg/m 3 ) and the fines (defined as particle 'smaller than 120 Mesh) level is below 5%.
  • Table 5 shows that catalyst (A) and (B) using silica with reactive surface have much higher activity than catalyst (C) , (D) , and (E) which do not use silica with a reactive surface.
  • the resins produced herein via the gas phase process exhibited the following characteristics: (1) narrower molecular weight distribution, (2) more uniform short chain branching distribution, (3) lower melting point (4) lower extractables, and (5) lower haze.
  • An example of the key resin characteristics of a 1.0 12, 0.918 density resin is shown below:
  • the LLDPE resins can be processed readily on commercial equipment without modification. They also offer superior properties compared to those resins produced using a commercial Ziegler/Natta catalyst. An example is given below:
  • Density ASTM D-1505 - a plaque is made and conditioned for one hour at 100°C to approach equilibrium crystallinity. Measurement for density is then made in a density gradient column; reported as g/cm3
  • MI Melt Index ASTM D-1238 - Condition E
  • Raw materials used in catalyst preparation included 505 g of Davison 952-1836 silica, 698 g of methylaluminoxane in toluene solution (30 wt% MAO), 7.148 g of bis(n- butylcyclopentadieny1) zirconium dichloride.
  • the steps of the catalyst preparation are set forth below: 1. Dehydrate the 955 silica at 250°C for 4 hours using air to purge. Then purge with nitrogen on cooling. 2. Transfer the silica to a mix-vessel.
  • the catalyst has the following analysis:
  • Example 3A To produce a polymer for cast film of 0.918 g/cm 3 density, 2.5 MI, 16 MFR, the following process conditions were employed: Fluidization velocity 1.7 ft/sec (0.52 m/s) Residence time 2.5 hours
  • the catalyst was that of Example 1A.
  • Table 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Cette invention se rapporte à un catalyseur de polymérisation ou de copolymérisation d'oléfines constitué de particules, lesquelles contiennent de la silice, un métal de transition et de l'aluminium. La silice est amorphe et poreuse, ses pores ont un volume compris entre 0,1 et 5 cm3/g et elle présente une concentration en groupes silanol qui est au moins égale à 0,7 mmole par gramme de silice. Le métal de transition et l'aluminium sont fournis par un mélange d'un métallocène et d'un alumoxane. Le volume total du métallocène et de l'alumoxane est inférieur ou égal au volume total des pores de la silice.
PCT/US1994/007232 1993-10-22 1994-06-24 Catalyseur de polymerisation ou de copolymerisation d'olefines WO1995011263A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002170883A CA2170883C (fr) 1993-10-22 1994-06-24 Catalyseur de polymerisation ou de copolymerisation d'olefines
KR1019960701986A KR960704941A (ko) 1993-10-22 1994-06-24 올레핀의 중합 또는 공중합 촉매(an olefin polymerization or copoly merization catalyst)
AU73179/94A AU697757B2 (en) 1993-10-22 1994-06-24 An olefin polymerization or copolymerization catalyst
EP94923257A EP0724603A4 (fr) 1993-10-22 1994-06-24 Catalyseur de polymerisation ou de copolymerisation d'olefines
JP7511749A JPH09504563A (ja) 1993-10-22 1994-06-24 オレフィン重合及び共重合用触媒

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14191193A 1993-10-22 1993-10-22
US141,911 1993-10-22

Publications (1)

Publication Number Publication Date
WO1995011263A1 true WO1995011263A1 (fr) 1995-04-27

Family

ID=22497773

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/007232 WO1995011263A1 (fr) 1993-10-22 1994-06-24 Catalyseur de polymerisation ou de copolymerisation d'olefines

Country Status (6)

Country Link
EP (1) EP0724603A4 (fr)
JP (1) JPH09504563A (fr)
KR (1) KR960704941A (fr)
AU (1) AU697757B2 (fr)
CA (1) CA2170883C (fr)
WO (1) WO1995011263A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016093A3 (fr) * 1994-11-23 1996-08-22 Exxon Chemical Patents Inc Procedes de realisation de catalyseurs sur support et systemes de catalyseurs ainsi obtenus
WO1997011775A3 (fr) * 1995-09-28 1997-06-05 Hoechst Ag Systeme de catalyseur supporte, son procede de production et son utilisation dans la polymerisation d'olefines
WO1999061489A1 (fr) * 1998-05-25 1999-12-02 Borealis Technology Oy Composition de catalyseur de polymerisation olefinique sur support
US6245705B1 (en) 1993-11-18 2001-06-12 Univation Technologies Cocatalysts for metallocene-based olefin polymerization catalyst systems
WO2001044319A3 (fr) * 1999-12-16 2001-12-27 Basell Technology Co Bv Processus et appareil permettant de produire des systemes de catalyseur sur support destines a la polymerisation olefinique
US6664352B1 (en) 1998-10-09 2003-12-16 Borealis Technology Oy Supported polymerization catalysts
EP0910471B1 (fr) * 1996-07-11 2004-10-20 Exxonmobil Oil Corporation Procede de preparation d'un catalyseur metallocene sur support pour la polymerisation d'olefines
WO2005014659A1 (fr) * 2003-08-07 2005-02-17 Eastman Chemical Company Procede de polymerisation et appareil associe
EP0678103B2 (fr) † 1993-11-05 2007-02-14 Borealis A/S Catalyseur de polymerisation d'olefines sur support, sa preparation et son utilisation
EP1834983A1 (fr) * 2006-03-14 2007-09-19 Ineos Europe Limited Films polymères
US7381783B2 (en) 1997-12-08 2008-06-03 Univation Technologies, Llc Polymerization catalyst systems, their use, their products and articles thereof
US8497330B2 (en) 1997-12-08 2013-07-30 Univation Technologies, Llc Methods for polymerization using spray dried and slurried catalyst
CN110557948A (zh) * 2017-05-17 2019-12-10 尤尼威蒂恩技术有限责任公司 铪络合物；负载型铪络合物；使用此类络合物形成聚合物的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914253A (en) * 1988-11-04 1990-04-03 Exxon Chemical Patents Inc. Method for preparing polyethylene wax by gas phase polymerization
US5001205A (en) * 1988-06-16 1991-03-19 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst
US5026797A (en) * 1987-10-22 1991-06-25 Mitsubishi Petrochemical Co., Ltd. Process for producing ethylene copolymers
EP0515132A2 (fr) * 1991-05-20 1992-11-25 Mitsui Petrochemical Industries, Ltd. Catalyseur et procédé de polymérisation d'oléfine
US5332706A (en) * 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU673048B2 (en) * 1992-12-28 1996-10-24 Mobil Oil Corporation Linear low density polyethylene film
FI96866C (fi) * 1993-11-05 1996-09-10 Borealis As Tuettu olefiinipolymerointikatalyytti, sen valmistus ja käyttö

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026797A (en) * 1987-10-22 1991-06-25 Mitsubishi Petrochemical Co., Ltd. Process for producing ethylene copolymers
US5001205A (en) * 1988-06-16 1991-03-19 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst
US4914253A (en) * 1988-11-04 1990-04-03 Exxon Chemical Patents Inc. Method for preparing polyethylene wax by gas phase polymerization
EP0515132A2 (fr) * 1991-05-20 1992-11-25 Mitsui Petrochemical Industries, Ltd. Catalyseur et procédé de polymérisation d'oléfine
US5332706A (en) * 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0724603A4 *

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0678103B2 (fr) † 1993-11-05 2007-02-14 Borealis A/S Catalyseur de polymerisation d'olefines sur support, sa preparation et son utilisation
US6245705B1 (en) 1993-11-18 2001-06-12 Univation Technologies Cocatalysts for metallocene-based olefin polymerization catalyst systems
WO1996016093A3 (fr) * 1994-11-23 1996-08-22 Exxon Chemical Patents Inc Procedes de realisation de catalyseurs sur support et systemes de catalyseurs ainsi obtenus
US5625015A (en) * 1994-11-23 1997-04-29 Exxon Chemical Patents Inc. Method for making supported catalyst systems and catalyst systems therefrom
WO1997011775A3 (fr) * 1995-09-28 1997-06-05 Hoechst Ag Systeme de catalyseur supporte, son procede de production et son utilisation dans la polymerisation d'olefines
US6271164B1 (en) * 1995-09-28 2001-08-07 Cornelia Fritze Supported catalyst system, process for its production and its use in polymerizing olefins
EP0910471B1 (fr) * 1996-07-11 2004-10-20 Exxonmobil Oil Corporation Procede de preparation d'un catalyseur metallocene sur support pour la polymerisation d'olefines
US7381783B2 (en) 1997-12-08 2008-06-03 Univation Technologies, Llc Polymerization catalyst systems, their use, their products and articles thereof
US8497330B2 (en) 1997-12-08 2013-07-30 Univation Technologies, Llc Methods for polymerization using spray dried and slurried catalyst
US8227564B2 (en) 1997-12-08 2012-07-24 Univation Technologies, Llc Ethylene copolymers and their uses
US7989564B2 (en) 1997-12-08 2011-08-02 Univation Technologies, Llc Catalyst systems and their use in polymerization processes
USRE40751E1 (en) 1997-12-08 2009-06-16 Univation Technologies, Llc Polymerization catalyst systems comprising substituted hafnocenes
US6720394B1 (en) 1998-05-25 2004-04-13 Borealis Technology Oy Supported olefin polymerization catalyst composition
WO1999061489A1 (fr) * 1998-05-25 1999-12-02 Borealis Technology Oy Composition de catalyseur de polymerisation olefinique sur support
US6664352B1 (en) 1998-10-09 2003-12-16 Borealis Technology Oy Supported polymerization catalysts
WO2001044319A3 (fr) * 1999-12-16 2001-12-27 Basell Technology Co Bv Processus et appareil permettant de produire des systemes de catalyseur sur support destines a la polymerisation olefinique
KR100738845B1 (ko) * 1999-12-16 2007-07-12 바셀 테크놀로지 캄파니 비이브이 올레핀 중합용 지지 촉매계를 제조하기 위한 방법 및 장치
CN1297340C (zh) * 1999-12-16 2007-01-31 巴塞尔技术有限公司 用来制备烯烃聚合的负载催化剂体系的方法和装置
US7041750B1 (en) 1999-12-16 2006-05-09 Basell Polyolefine Gmbh Process and apparatus for making supported catalyst systems for olefin polymerization
US8063158B2 (en) 2003-08-07 2011-11-22 Westlake Longview Corp. Polymerization process and associated apparatus
US8088334B1 (en) 2003-08-07 2012-01-03 Westlake Longview Corp. Polymerization process and associated apparatus
WO2005014659A1 (fr) * 2003-08-07 2005-02-17 Eastman Chemical Company Procede de polymerisation et appareil associe
WO2007104924A1 (fr) * 2006-03-14 2007-09-20 Ineos Europe Limited Films de polymère
EP1834983A1 (fr) * 2006-03-14 2007-09-19 Ineos Europe Limited Films polymères
US8338551B2 (en) 2006-03-14 2012-12-25 Ineos Europe Limited Polymer films
CN101443391B (zh) * 2006-03-14 2014-03-05 英尼奥斯欧洲有限公司 聚合物薄膜
CN110557948A (zh) * 2017-05-17 2019-12-10 尤尼威蒂恩技术有限责任公司 铪络合物；负载型铪络合物；使用此类络合物形成聚合物的方法

Also Published As

Publication number Publication date
AU7317994A (en) 1995-05-08
KR960704941A (ko) 1996-10-09
EP0724603A4 (fr) 1997-01-08
CA2170883C (fr) 2005-08-16
JPH09504563A (ja) 1997-05-06
EP0724603A1 (fr) 1996-08-07
AU697757B2 (en) 1998-10-15
CA2170883A1 (fr) 1995-04-27

Similar Documents

Publication Publication Date Title
US5608019A (en) Temperature control of MW in olefin polymerization using supported metallocene catalyst
US5602067A (en) Process and a catalyst for preventing reactor fouling
US5332706A (en) Process and a catalyst for preventing reactor fouling
US6090740A (en) Supported metallocene catalyst systems
EP0728151B1 (fr) Procede de polymerisation ou de copolymerisation d'ethylene
KR100355623B1 (ko) 촉매조성물을사용한에틸렌중합체및공중합체의제조방법
CA2170883C (fr) Catalyseur de polymerisation ou de copolymerisation d'olefines
WO1998018842A1 (fr) Copolymeres lldpe

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994923257

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2170883

Country of ref document: CA

WWP Wipo information: published in national office

Ref document number: 1994923257

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1994923257

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载