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WO1999035173A1 - Catalyseur pour la production d'homopolymeres et de copolymeres d'ethylene - Google Patents

Catalyseur pour la production d'homopolymeres et de copolymeres d'ethylene Download PDF

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Publication number
WO1999035173A1
WO1999035173A1 PCT/DE1998/003685 DE9803685W WO9935173A1 WO 1999035173 A1 WO1999035173 A1 WO 1999035173A1 DE 9803685 W DE9803685 W DE 9803685W WO 9935173 A1 WO9935173 A1 WO 9935173A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
alkyl
aryl
catalyst system
fluorine
Prior art date
Application number
PCT/DE1998/003685
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German (de)
English (en)
Inventor
Diana ÖZDEMIR
Markus Schopf
Original Assignee
Elenac Gmbh
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Filing date
Publication date
Application filed by Elenac Gmbh filed Critical Elenac Gmbh
Publication of WO1999035173A1 publication Critical patent/WO1999035173A1/fr

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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
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 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

Definitions

  • the present invention relates to a heterogeneous (insoluble) catalyst which can advantageously be used in the ethylene polymerization and copolymerization of ethylene and 1-olefins.
  • EP-A-069 951 discloses processes for the production of polyolefms with the aid of homogeneous (soluble) catalyst systems.
  • the known catalyst systems consist of a transition metal component of the metallocene type and a cocatalyst component, an oligomeric aluminum compound of the aluminoxane type, usually methylaluminoxane (MAO), which give narrowly distributed polymers or copolymers with high activity.
  • MAO methylaluminoxane
  • the catalyst preparation procedure has the disadvantage that relatively large amounts of a solvent or suspending agent (generally toluene) are used; to obtain the ready-to-use catalyst, these must be removed by decanting and evacuating and either discarded or purified by distillation and / or adsorption before being reused.
  • a solvent or suspending agent generally toluene
  • catalyst production processes have been proposed in which the amount of solvent used is reduced, so that the decanting step for separating off the solvent is eliminated.
  • a drying step which reduces the residual solvent content on the solid catalyst must follow the catalyst preparation.
  • An excessive amount of solvent leads to easy washing out of catalyst constituents during the polymerization and thus to the formation of deposits, an insufficient amount can result in the formation of electrostatic product deposits in the reactor as well as a lower long-term stability of the solid catalyst during the polymerization.
  • the object of the present invention was to find a supported metallocene catalyst which can be stored for at least 10 weeks and which has very good activity in the ethylene homopolymerization or copolymerization in the suspension process and shows product morphology, but at the same time does not cause any annoying deposit formation.
  • a metallocene catalyst system which contains a metallocene compound, a cocatalyst based on an aluminum or boron compound, a support material and a solvent and whose characteristic feature is that, based on its total weight, it has a solvent content in Has a range from 1 to 20% by weight, preferably from 5 to 10% by weight.
  • the amount of solvent used is chosen such that no suspension of the insoluble support material in the solvent occurs during its production, but on the other hand there is a uniform wetting of the support material and thus a homogeneous distribution of the catalyst on the support is guaranteed.
  • An essential parameter for this is the ratio between the amount of solvent used in the catalyst production and the free pore volume of the support material. The ratio of these sizes is particularly suitable if, when solution and carrier material are combined, a homogeneous, gelatinous mass which no longer flows is formed.
  • the appropriate volume of solvent depends on the nature of the solvent and the
  • Carrier material and usually moves in the range of 1.0 to 3.0 times the pore volume of the carrier material.
  • the pore volume is a characteristic of spherical SiO 2 carriers and is usually specified by the manufacturer. The exact determination of the pore volume is carried out by titration with water. A sample of carrier material is heated to a temperature of 200 ° C over a period of 2 hours. An amount of 10 to 40 g is then weighed into a closable container and an amount of water is then added which corresponds to approximately 80% of the pore volume to be expected. After shaking vigorously, the mixture is then cooled to room temperature, after which further portions of water are added until a saturated gel has formed and until the water just begins to wet the surface of the carrier material. Between the individual additions of water, shake vigorously again and again to evenly distribute the water. The value for the pore volume then results from the amount of water in [ml] divided by the original weight of the sample in [g].
  • the metallocene catalyst system according to the invention thus contains at least one metallocene compound, at least one cocatalyst, at least one support material and at least one solvent.
  • Suitable metallocene compounds are, for example, bridged or unbridged biscyclopentadienyl complexes, such as those e.g. in EP-A-129 368, EP-A-561 479, EP-A-545 304 and EP-A-576 970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes which e.g.
  • EP-A-416 815 multinuclear cyclopentadienyl complexes as described in EP-A-632 063, ⁇ -ligand-substituted tetrahydropentalenes as described in EP-A-659 758 or ⁇ -ligand-substituted tetrahydroindenes as in EP-A A-661 300.
  • Preferred metallocene starting compounds are unbridged or bridged metallocene compounds of the formula I,
  • M 1 is a metal of III., IV., V. or VI.
  • R 1 are identical or different and are a hydrogen atom or SiR 3 3 , in which R 3, identical or different, is a hydrogen atom or a C, -C 40 -carbon-containing group such as C, -C 20 alkyl, C, -C ] 0 fluoroalkyl, C, -C I0 alkoxy, C 6 -C 20 aryl, C 6 -C 10 -
  • R 1 is a C, -C 30 - carbon-containing group such as C, -C 25 - alkyl, for example methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 alkenyl, C 3 -C ] 5 - alkylalkenyl, C 6 -C 24- aryl, C 5 -C 24 heteroaryl such as pyridyl, furyl or quinolyl, C 7 - C 30 arylalkyl, C 7 -C 30 alkylaryl, fluorine-containing C, -C 25 alkyl, fluorine-containing C 6 -C 24 - Aryl,
  • Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
  • Z examples are groups M 2 R 4 R 5 , where M 2 is carbon, silicon, germanium or tin and R 4 and R 5, identical or different, are a C, -C 20 -hydrocarbon-containing group, such as C r C 10 alkyl, C 6 -C 14 aryl or trimethylsilyl.
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, (C 6 H 5 ) 2 Ge, (C 6 H 5 ) 2 Sn , (CH 2 ) 4 Si, CH 2 Si (CH 3 ) 2 , oC 6 H 4 or 2,2 ' - (C 5 H 4 ) 2 .
  • Z can also form a mono- or polycyclic ring system with one or more radicals R 1 and / or R 2 .
  • metallocene starting compounds are:
  • any compound which can convert the neutral metallocene into a cation and stabilize it is suitable as a cocatalyst in the process according to the invention.
  • the cocatalyst or the anion formed from it should not undergo further reactions with the metallocenium cation formed (see EP-A-427 697).
  • An aluminum compound and / or a boron compound is preferably used as the cocatalyst.
  • the boron compound preferably has the formula R 18 X NH 4 _ X BR 19 4 , R 18 X PH 4 .
  • X BR , 9 4 , R 18 3 CBR 19 4 or BR , 9 3 where x is a number from 1 to 4, preferably 3, the radicals R 18 are identical or different, preferably identical, and C, -C 10 Are alkyl or C 6 -C 18 aryl, or two radicals R 18 together with the atoms connecting them form a ring, and the radicals R 19 are identical or different, preferably identical, and are C 6 -C 18 aryl, which can be substituted by alkyl, haloalkyl or fluorine.
  • R 18 represents ethyl, propyl, butyl or phenyl and R 19 represents phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP-A-277 003, EP-A-277 004 and EP-A- 426 638).
  • An aluminum compound such as aluminoxane and / or an aluminum alkyl is preferably used as the cocatalyst.
  • An aluminoxane in particular of the formula Ha for the linear type and / or of the formula Ilb for the cyclic type, is particularly preferably used as the cocatalyst, the radicals R 20 in the formulas Ha and Ilb being the same or different and hydrogen or one
  • C, -C 20 hydrocarbon group such as a C, -C 18 alkyl group, a C 6 -C 18 aryl group or benzyl
  • p is an integer from 2 to 50, preferably 10 to 35.
  • the R 20 radicals are preferably the same and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
  • R 20 radicals are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in a numerical proportion of 0.01 to 40% (of the R 20 radicals).
  • aluminoxane solutions have in common a changing content of unreacted aluminum starting compound, which is present in free form or as an adduct. It is possible to preactivate the metallocene compound with a cocatalyst, in particular an aluminoxane, before use in the polymerization reaction. This significantly increases the polymerization activity and ensures a firm and irreversible fixation of the catalyst components on the support material.
  • the metallocene compound is preferably preactivated in solution.
  • the metallocene compound is preferably dissolved in a solution of the aluminoxane in an inert solvent.
  • Suitable solvents are aromatic hydrocarbons such as benzene or toluene or polar halogenated hydrocarbons such as chlorobenzene, methyl chloride, methylene chloride or chloroform. Toluene is preferably used.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total amount of solution.
  • the metallocene is used in an amount of 10 3 to 1 mol per mol of aluminoxane, preferably 5-10 3 to 2 10 2 mol per mol of aluminoxane.
  • the preactivation time is 5 minutes to 60 hours, preferably 5 minutes to 12 hours. One works at a temperature of -78 to 100 ° C, preferably 0 to 80 ° C.
  • the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, silica, other inorganic oxides or finely divided polymer powders such as polyolefms.
  • Inorganic oxides of elements from groups 2, 3, 4, 5, 13, 14, 15 and 16 of the periodic table of the elements are suitable.
  • preferred oxides as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred carriers are MgO, ZrO 2 or B 2 O 3 , to name just a few.
  • the carrier materials used have a specific surface area in the range from 10 m 2 / g to 1000 m 2 / g, a pore volume in the range from 0.1 ml / g to 5 ml / g and an average Particle size from 1 ⁇ m to 500 ⁇ m.
  • Carriers with a specific surface area in the range from 50 m 2 / g to 500 ⁇ / g, a pore volume in the range between 0.5 ml / g and 3.5 ml / g and an average particle size in the range from 5 ⁇ m to 350 are preferred ⁇ m.
  • Carriers with a specific surface area in the range from 200 nm / g to 400 m 2 / g, a pore volume in the range between 0.8 ml / g to 3.0 ml / g and an average particle size of 10 ⁇ m to 200 ⁇ m are particularly preferred .
  • the preactivation solution containing the metallocene compound, cocatalyst and solvent and the carrier material are combined, dilution of the preactivation solution with a suitable inert solvent ensures that the ratio of the volume of the preactivation solution to the pore volume of the carrier material is in a suitable range .
  • the ratio of the volume of the preactivation solution to the pore volume is suitable if a non-flowable, homogeneous, gelatinous mass is formed when combined.
  • the appropriate volume of the preactivation solution depends on the nature of the solvent and the
  • Carrier material normally ranges from 1.0 to 3.0 times the pore volume of the carrier material.
  • Solvents suitable according to the invention are aromatic hydrocarbons such as benzene or toluene or polar halogenated hydrocarbons such as chlorobenzene, methyl chloride, methylene chloride or chloroform. Toluene is preferably used.
  • the supported catalyst system can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before it is used in a polymerization process. This is what is supported
  • the prepolymerized catalyst system can then be dried until it is free-flowing.
  • the suspension can also be used directly for the polymerization be used.
  • Another possible embodiment variant is to prepolymerize the catalyst system in the gas phase. For this purpose, at least one olefin of the above meaning is passed through the catalyst system in powder form with stirring.
  • a small amount of a 1-olefin, such as styrene can be added as an activity-increasing component or an antistatic during or after the preparation of the supported catalyst system.
  • the present invention also relates to a process for the preparation of a polyolefin by polymerizing one or more olefins in the presence of the catalyst system according to the invention comprising at least one metallocene of the formula I.
  • the term polymerization is understood to mean homopolymerization and also copolymerization.
  • the supported catalyst system can be used as a scavenger for the polymerization of olefins in combination with an aluminum alkyl or an aluminoxane.
  • the soluble aluminum components are added to the monomer or the suspending agent and are used to purify the polymerization batch from substances which can impair the catalyst activity.
  • the amount of aluminum component added depends on the quality of the monomers and suspending agents used.
  • Aluminum alkyls such as trimethyl aluminum (TMA), triethyl aluminum (TEA) or triisobutyl aluminum (TIBA) are preferably used as scavengers.
  • olefins examples include 1-olefins having 2 to 40, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methyl norbornene.
  • Ethene is preferably homopolymerized in the process according to the invention, or ethene with one or more 1-olefins having 4 to 20 C atoms, such as butene or hexene, and / or one or more dienes having 4 to 20 C atoms, such as 1, 4 -Butadien, Norbornadien,
  • 1-Butene and 1-hexene are preferably used as comonomers.
  • the polymerization is carried out at a temperature of -60 ° C to 300 ° C, preferably 50 ° C to 200 ° C, most preferably 65 ° C to 90 ° C.
  • the pressure is 0.5 bar to 2000 bar, preferably 5 bar to 64 bar, very particularly preferably 5 bar to 10 bar.
  • the catalyst system according to the invention can be used both in a suspension polymerization and in a gas phase polymerization.
  • a suspension process is preferably used.
  • the polymerization proceeds with high activity without formation of deposits and results in a polymer with a uniform grain morphology.
  • Examples 1-3 describe for three different metallocene compounds the preparation of supported catalysts with the amount of solvent according to the invention during catalyst preparation (characterized by the ratio of the volume of the
  • Preactivation solution for the pore volume of the support material Preactivation solution for the pore volume of the support material) and residual solvent content according to the invention of the finished catalyst.
  • Comparative example 3A describes a catalyst which has too little residual solvent content. Comparative example 3B describes a catalyst which has an excessively high residual solvent content.
  • Comparative Example 3C describes a catalyst in which the amount of solvent used was too small.
  • Comparative example 3D describes a catalyst in the production of which an excessive amount of solvent was used.
  • test polymerizations 1 and 2 are carried out within 1-3 days after the preparation.
  • Another test polymerization (Polymerization 3) is carried out after 60-90 days after the preparation.
  • Tables 1 and 2 summarize the characteristic features of the catalysts (solvent / pore volume ratio in catalyst synthesis and residual toluene content of the finished catalyst) and the results of the test polymerizations.
  • the size "KZAred” is used, which indicates how much polyethylene per mmol of Zr and bar of ethylene pressure per hour with the respective
  • Carrier material XPO 2402 based on silica from Grace The used The carrier material has a pore volume of 1.50 ml / g. The solution has 2.5 times the pore volume of the silica. A no longer flowable, homogeneous, gelatinous mass is created. The stirring is stopped and the catalyst is dried under high vacuum at room temperature. After 4 hours, the drying is ended at a toluene content of the catalyst of 9%.
  • TIBA triisobutylaluminum
  • the catalyst is prepared analogously to Example 1 from 790 mg Me 2 Si (2-Me-4-Ph-Ind) 2 ZrCl 2 , 38 ml MAO solution, 42 g of the carrier XPO 2402 and 93 ml toluene.
  • the solution has 2.1 times the pore volume of the carrier material.
  • a residual toluene content of 10% is set by drying.
  • the catalyst is prepared analogously to Example 1 from 780 mg (n-Bu-Cp) 2 ZrCl 2 , 59 ml of MAO solution, 42 g of the carrier XPO 2402 and 110 ml of toluene.
  • the solution has 2.7 times the pore volume of the carrier material.
  • a residual toluene content of 8% is set by drying.
  • the catalyst is prepared analogously to Example 1 from 780 mg (n-Bu-Cp) 2 ZrCl 2 , 59 ml of MAO solution, 42 g of the carrier XPO 2402 and 110 ml of toluene.
  • the solution has 2.7 times the pore volume of the carrier material.
  • the catalyst is dried to constant weight, corresponding to a residual toluene content of 0%.
  • the catalyst is prepared analogously to Example 1 from 780 mg (n-Bu-Cp) 2 ZrCl 2 , 59 ml of MAO solution, 42 g of the carrier XPO 2402 and 110 ml of toluene.
  • the solution has 2.7 times the pore volume of the carrier material.
  • a residual toluene content of 28% is set by drying.
  • the catalyst is prepared analogously to Example 1 from 740 mg (n-Bu-Cp) 2 ZrCl 2 , 56 ml of MAO solution, 40 g of the carrier XPO 2402 and 30 ml of toluene.
  • the solution has 1.4 times the pore volume of the carrier material.
  • a residual toluene content of 7% is set by drying.
  • no formation of deposits was found in the reactor.
  • the microscopic examination of the products shows a non-uniform spherical morphology, it can be seen that not all silica particles are fragmented in the course of the polymerization.
  • the catalyst is prepared analogously to Example 1 from 810 mg (n-Bu-Cp) 2 ZrCl 2 , 61 ml of MAO solution, 44 g of the XPO 2402 support and 200 ml of toluene.
  • the solution has 4 times the pore volume of the carrier material.
  • the carrier material is stirred into the solution, a suspension is formed in which a separation between the liquid and solid phases can be observed.
  • a residual toluene content of 5% is set by drying.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un catalyseur hétérogène pour la synthèse de polyoléfines, contenant un composé métallocène, un cocatalyseur à base d'un composé d'aluminium ou de bore, un matériau support et un solvant. Ce catalyseur présente une teneur en solvant comprise entre 1 et 20 % en poids, par rapport à son poids total. De façon avantageuse, ce catalyseur permet de produire des homopolymères ou des copolymères d'éthylène et de 1-oléfines.
PCT/DE1998/003685 1997-12-31 1998-12-11 Catalyseur pour la production d'homopolymeres et de copolymeres d'ethylene WO1999035173A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997158306 DE19758306B4 (de) 1997-12-31 1997-12-31 Katalysator für die Polyolefinsynthese
DE19758306.7 1997-12-31

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WO1999035173A1 true WO1999035173A1 (fr) 1999-07-15

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109666090A (zh) * 2017-10-16 2019-04-23 中国石油化工股份有限公司 一种用于烯烃聚合反应的负载茂金属催化剂、制备方法及应用
CN110964132A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 复合载体分段原位负载型非茂金属催化剂及其制备方法
CN110964137A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 镁化合物负载型非茂金属催化剂、其制备方法及其应用
CN110964139A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 镁单载体原位负载型非茂金属催化剂、其制备方法及应用
CN110964136A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 复合载体负载型非茂金属催化剂、其制备方法及其应用
CN110964138A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 镁单载体分段原位负载型非茂金属催化剂及其制备方法
CN110964140A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 一种原位负载型非茂金属催化剂、其制备方法及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0598543A2 (fr) * 1992-11-10 1994-05-25 Mitsubishi Chemical Corporation Procédé de production de polymères d'alpha-oléfines
WO1994021691A1 (fr) * 1993-03-25 1994-09-29 Mobil Oil Corporation Procede de formation d'une resine granulaire
WO1996000245A1 (fr) * 1994-06-24 1996-01-04 Exxon Chemical Patents Inc. Systemes catalyseurs de polymerisation, leur production et leur utilisation
WO1996018661A1 (fr) * 1994-12-15 1996-06-20 Exxon Chemical Patents Inc. Systemes de catalyseur de polymerisation, procedes de production et d'utilisation de ces derniers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI96866C (fi) * 1993-11-05 1996-09-10 Borealis As Tuettu olefiinipolymerointikatalyytti, sen valmistus ja käyttö
CN1064641C (zh) 1994-07-20 2001-04-18 柯尼格及包尔-艾伯特公开股份有限公司 在运转中更换备用纸带卷而准备纸带卷端头的方法与装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0598543A2 (fr) * 1992-11-10 1994-05-25 Mitsubishi Chemical Corporation Procédé de production de polymères d'alpha-oléfines
WO1994021691A1 (fr) * 1993-03-25 1994-09-29 Mobil Oil Corporation Procede de formation d'une resine granulaire
WO1996000245A1 (fr) * 1994-06-24 1996-01-04 Exxon Chemical Patents Inc. Systemes catalyseurs de polymerisation, leur production et leur utilisation
WO1996018661A1 (fr) * 1994-12-15 1996-06-20 Exxon Chemical Patents Inc. Systemes de catalyseur de polymerisation, procedes de production et d'utilisation de ces derniers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109666090A (zh) * 2017-10-16 2019-04-23 中国石油化工股份有限公司 一种用于烯烃聚合反应的负载茂金属催化剂、制备方法及应用
CN109666090B (zh) * 2017-10-16 2021-09-21 中国石油化工股份有限公司 一种用于烯烃聚合反应的负载茂金属催化剂、制备方法及应用
CN110964132A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 复合载体分段原位负载型非茂金属催化剂及其制备方法
CN110964137A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 镁化合物负载型非茂金属催化剂、其制备方法及其应用
CN110964139A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 镁单载体原位负载型非茂金属催化剂、其制备方法及应用
CN110964136A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 复合载体负载型非茂金属催化剂、其制备方法及其应用
CN110964138A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 镁单载体分段原位负载型非茂金属催化剂及其制备方法
CN110964140A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 一种原位负载型非茂金属催化剂、其制备方法及其应用
CN110964132B (zh) * 2018-09-28 2023-08-04 中国石油化工股份有限公司 复合载体分段原位负载型非茂金属催化剂及其制备方法

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