WO2015080523A1 - Procédé de préparation d'un catalyseur métallocène supporté - Google Patents

Procédé de préparation d'un catalyseur métallocène supporté Download PDF

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WO2015080523A1
WO2015080523A1 PCT/KR2014/011580 KR2014011580W WO2015080523A1 WO 2015080523 A1 WO2015080523 A1 WO 2015080523A1 KR 2014011580 W KR2014011580 W KR 2014011580W WO 2015080523 A1 WO2015080523 A1 WO 2015080523A1
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group
carbon atoms
alkyl
supported
aryl
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PCT/KR2014/011580
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English (en)
Korean (ko)
Inventor
이승미
최이영
이기수
송은경
권헌용
조민석
홍대식
권현지
승유택
정동훈
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주식회사 엘지화학
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Priority claimed from KR1020140167732A external-priority patent/KR101721194B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2016526289A priority Critical patent/JP6314223B2/ja
Priority to EP14865686.1A priority patent/EP3050904B1/fr
Priority to CN201480064747.1A priority patent/CN105980417B/zh
Priority to US15/033,866 priority patent/US9657119B2/en
Publication of WO2015080523A1 publication Critical patent/WO2015080523A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/05—Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/65925—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 two cyclopentadienyl rings being mutually non-bridged

Definitions

  • the present invention relates to a method for preparing a highly active supported metallocene catalyst having a high density.
  • Metallocene catalysts used in the production of polyethylene using slurry and g as -phase synthesis processes must be firmly immobilized on a suitable carrier to avoid reactor fouling due to leaching.
  • the apparent density of the polymer is closely related to the reactor unit productivity, not only the catalyst activity but also the high density of the polymer should be high.
  • supported metallocene catalysts In order to prepare supported metallocene catalysts, it is common to use a highly active metallocene catalyst to increase the catalytic activity and to increase the amount of aluminoxane, which is a promoter, and to carry the supported metallocene catalyst.
  • polymerization occurs on the surface of the carrier first, and the resulting polymer is crystallized to inhibit the diffusion of the next monomer (momomer di f fus ion) to form a hollow polymer, thereby lowering the density of the hook.
  • An object of the present invention is to provide a method for preparing a supported metallocene catalyst capable of producing a polyolefin polymer with improved apparent density of a polymer while maintaining high active catalyst properties, and a method for preparing a polyolefin using the same.
  • the present invention comprises the steps of preparing a silica carrier; Contacting the silica carrier with an alkylaluminoxane as a promoter component to support the alkylaluminoxane on the inside and the surface of the silica carrier; And sequentially supporting one or more metallocene compounds on the silica carrier on which the alkylaluminoxane is supported, wherein the alkali aluminoxane is a supported metal supported on the silica carrier by a split dosing method at different temperatures.
  • a method for preparing a rosene catalyst is provided.
  • the alkylaluminoxane may be supported on the silica carrier by a partial dosing method in which a part of the total input amount is first introduced at a temperature of 50 ° C. or higher, and the remainder of the total input amount is secondary input at a temperature of 40 ° C. or less.
  • the silica carrier on which the alkylaluminoxane is loaded 50 to 90% by weight of the total amount of the total amount of the alkylaluminoxane is first supported on the silica carrier at 50 ° C to 150 ° C. c to
  • the remaining alkylaluminoxane may be obtained by dipping the remaining alkylaluminoxane in a silica carrier at 40 ° C. and proceeding with a post reaction.
  • the supported metallocene catalyst according to the method of the present invention when the carrier catalyst particles are cut in the cross-section, the outer layer comprising a point up to one third of the total diameter of the particles from each surface toward the center portion, and the particles A silica carrier comprising an inner layer comprising the remaining ' part from one third of the point to an inner center, wherein the alkylaluminoxane is supported on the inside and the surface of the carrier; At least one metallocene compound supported on the silica carrier, wherein the Al / Si content ratio (weight%) of the inner layer is at least 65% of the Al / Si content ratio (weight%) of the outer layer.
  • the Al / Si element content ratio (weight%) of the inner layer is preferably 90 to 150% of the Al / Si element content ratio (weight%) of the outer layer.
  • the silica carrier may be one or more selected from the group consisting of silica, silica-alumina and silica-magnesia.
  • alkyl aluminoxane is methyl aluminoxane, ethyl aluminoxane, It may be at least one member selected from the group consisting of butyl aluminoxane and isobutyl aluminoxane.
  • the present invention may further include a step of supporting a borate compound as a system co-catalyst on a silica carrier on which an alkylaluminoxane and at least one metallocene compound are supported.
  • the borate compound may include a borate compound in the form of a trisubstituted ammonium salt, a borate compound in the form of a dialkyl ammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt.
  • the present invention provides a method for producing a polyolefin comprising the step of subjecting the olefin monomer in the presence of a supported metallocene catalyst according to the above method.
  • the polyolefin can have a hanging density of 0.1 to 0.8 g / ciu J.
  • the polyolefin may have a settling efficiency (sett ling ef fi ciency) defined by the following formula 20 to 80%.
  • the alkylaluminoxane cocatalyst penetrates deep inside the pores of the silica carrier than before. And a substantial amount on the outer surface thereof, it is possible to produce a polyolefin polymer having excellent apparent density while maintaining high activity.
  • Figure 1 shows the results of the shape analysis through the depth profile (depth prof i le) in the supported catalyst of Comparative Example 1.
  • Figure 2 shows the results of the shape analysis through the depth profile (depth prof i le) inside the supported catalyst of Example 2.
  • the meaning of “comprising” as used in the specification of the present invention embodies a specific characteristic, a region, an integer, a step, an operation, an element and / or a component, and another characteristic, a region, an integer, a step, an operation, an element and / or It does not exclude the presence or addition of ingredients.
  • a method of preparing a supported metallocene catalyst according to embodiments of the present invention will be described.
  • the supported catalyst particles include a silica carrier supported with alkylaluminoxane as a promoter.
  • the portion including up to one third of the total diameter of the particles from each surface toward the center portion is defined as the outer layer, 1/3 points of the particles
  • the remaining portion from to the inner center, ie, the portion containing two thirds of the remaining inner center, is defined as the inner layer.
  • the inner layer comprises a portion which is 70% of the longest radius from the center of the silica carrier in the supported metallocene catalyst
  • the outer layer comprises the remaining outer portion of the silica carrier.
  • the inside of the silica carrier mentioned in the present invention includes pores.
  • water content of the carrier is defined as a percentage of the weight of water contained in the carrier relative to the total weight of the carrier.
  • the supported metallocene catalyst of the present invention means a catalyst on which one or more metallocene compounds are supported.
  • the supported metallocene catalyst of the present invention may further include a borate-based compound as a second cocatalyst.
  • the present invention relates to a method for preparing a supported metallocene catalyst, which can produce a polyolefin polymer having improved apparent density of a polymer while maintaining high active catalyst properties.
  • preparing a silica carrier The silica Contacting the carrier with an alkylaluminoxane as a promoter component to support the alkylaluminoxane on and inside the silica carrier; And sequentially supporting one or more metallocene compounds on the silica carrier on which the alkylaluminoxane is supported, wherein the alkali aluminoxane is a supported metal supported on the silica carrier by a split dosing method at different temperatures.
  • a method for preparing a rosene catalyst is provided.
  • the present invention is characterized in that the preparation of the supported metallocene catalyst, the cocatalyst is divided into a silica carrier so that the promoter is distributed in a relatively large amount, the temperature range is different.
  • the present invention can provide a supported metallocene catalyst having a specific parameter with respect to the content of Al / Si in the carrier.
  • the present invention comprises an outer layer comprising up to one third of the total diameter of the particle from each surface towards the center when the carrier catalyst particles are cut in cross section, and from one third point to the inner center of the particle.
  • a silica carrier comprising an inner layer comprising the remainder of the alkyl carrier, the alkylaluminoxane supported on the inside and the surface of the carrier; At least one metallocene compound supported on the silica carrier; wherein the Al / Si content ratio (weight%) of the inner layer is at least 65% of the Al / Si content ratio (weight 3 ⁇ 4) of the outer layer , Supported metallocene catalyst can be provided.
  • the metallocene catalyst according to the present invention is characterized in that a large amount of alkylaluminoxane penetrates and chemically bonds to the inside and pores of the silica carrier as a whole, and a considerable amount of alkylaluminoxane is physically bonded to the surface. That is, conventionally, alkyl aluminoxane that penetrates into the carrier and has a chemical bond is small.
  • the present invention is to further support the promoter in the inner layer by a method of dividing the alkyl aluminoxane when supported on the carrier. Therefore, the supported metallocene catalyst of the present invention contains a large amount of alkylaluminoxane in the inner layer in the configuration consisting of the inner layer and the outer layer, thereby improving the apparent density and controlling the catalyst activity easily.
  • the Al / Si content ratio (weight%) of the inner layer is Al / Si of the outer layer. It becomes 65% or more of an element content ratio (weight%), Preferably it is 90 to 150%.
  • the aluminum of alkylaluminoxane is silica It means that the amount penetrated deeply to the inner layer part of the carrier is large.
  • the metallocene compound may be one or more metallocene compounds well known in the art to be described later.
  • Such a method for preparing a supported metallocene catalyst of the present invention comprises the steps of preparing a silica carrier; Contacting the silica carrier with an alkylaluminoxane as a promoter component to support the alkylaluminoxane on the inside and the surface of the silica carrier; And sequentially supporting one or more metallocene compounds on the silica carrier on which the alkylaluminoxane is supported.
  • the present invention proceeds to prepare a silica carrier.
  • the present invention selects silica carriers having morphologies suitable for the Philips loop slurry process.
  • the present invention optimizes the binding of alkylaluminoxanes, which are supported metallocene catalysts and promoters, by selectively controlling the amount of silane groups and siloxane groups on the silica carrier through cal cinat ions conditions.
  • the temperature can range from the silver that loses water on the surface of the silica to the temperature where the 0H group disappears completely on the surface.
  • the firing conditions of the silica carrier is preferably baked at a temperature of 100 to 700 ° C. Through the firing, the water content of the silica carrier is preferably 0.1 to 7% by weight.
  • the carrier may include a hydroxyl group of 0.5 to 5 kPa / g, preferably 0.7 to 2 kPa / g, on the surface of the carrier.
  • Such a carrier may be at least one member selected from the group consisting of silica, silica-alumina, and silica-magnesia, preferably silica.
  • any carrier that satisfies the above water content range can be used without limitation.
  • the trialkylaluminum may be one or more selected from the group consisting of trimethylaluminum (TMA1), triethylaluminum (TEA1) and tributylaluminum (TBA1), preferably triethylaluminum ( TEA1).
  • TMA1 trimethylaluminum
  • TEA1 triethylaluminum
  • TSA1 tributylaluminum
  • TEA1 triethylaluminum
  • the solvent examples include aliphatic hydrocarbons such as nucleic acids, pentane and heptane; Aromatic hydrocarbons such as toluene, benzene; Hydrocarbons substituted with chlorine atoms such as dichloromethane; Most organic solvents such as ethers such as diethyl ether and tetrahydrofuran (THF); acetone and ethyl acetate can be used.
  • a nucleic acid, heptane, toluene or dichloromethane may be used as the solvent.
  • the surface treatment step of the carrier may be performed at a temperature condition of 0 to 120 ° C, preferably 10 to 100 ° C, more preferably 30 to 90 ° C in terms of process efficiency improvement.
  • the amount of trialkylaluminum reacted on the surface of the carrier by the above step is not particularly limited, but the molar ratio of alkylaluminoxane to trialkylaluminum is 1:10 to 1:20 in relation to alkylaluminoxane, which will be described later. It may be preferably performed to be 1:12 to 1:18. That is, the molar ratio of alkylaluminoxane to trialkylaluminum is preferably 1: 10 or more, in order to be able to properly react with the water on the surface of the carrier, and a silanol group on the surface of the carrier, which is reacted with alkylaluminoxane. In order not to be removed, the molar ratio is preferably 1:20 or less.
  • the additional surface treatment step of the carrier is a reaction and adding a solvent and a carrier in a reaction vessel, and then mixed with trialkylaluminum, reacting for 30 minutes to 3 hours in the above-described temperature range It can be carried out by the method.
  • the present invention is not limited thereto.
  • the method for producing a supported metallocene catalyst of the present invention comprises the step of supporting the alkyl aluminoxane on the inside and the surface of the silica carrier by contacting the silica carrier with alkylaluminoxane as a promoter component. do.
  • the present invention is characterized by splitting at different temperatures while changing the temperature from high temperature to low temperature when the alkylaluminoxane is supported on a silica carrier. That is, the alkylaluminoxane is supported on the silica carrier by a partial dosing method in which a part of the total input amount is first injected from silver and the remainder of the total input amount is secondly injected at low temperature.
  • the high temperature may include a range of 50 degrees or more, preferably 50 to 150 degrees
  • the low silver may include a range of 40 degrees or less, or a range of ⁇ 10 degrees to 40 degrees.
  • the alkylaluminoxane is divided into a first part of the total input amount at a temperature of 50 ° C or more, and the remainder of the total input amount is 4 (the second input at a temperature of C or less)
  • a method for preparing a supported metallocene catalyst supported on a silica carrier by a charging method is provided.
  • the silica carrier on which the alkylaluminoxane is loaded 50 to 90% by weight of the total amount of the alkylaluminoxane content at 50 ° C to 150 ° C 1 to the silica carrier Carrying the pre-reaction by the secondary support, the remaining alkylaluminoxane at -10 ° C to 40 ° C may be obtained by carrying out the post-reaction by supporting the second alkyl in the silica carrier.
  • the silica obtained in the above step is contacted with alkylaluminoxane as a promoter component.
  • the contacting method of the present invention by injecting the alkyl aluminoxane by dividing the alkyl aluminoxane into the silica carrier over the secondary as described above, so as to penetrate the alkyl aluminoxane in a larger amount than the existing as described above.
  • a considerable amount of alkylaluminoxane is supported on the surface.
  • this method provides a silica carrier consisting of an inner layer of the silica carrier on which the alkylaluminoxane is supported on the inside and the surface and an outer layer surrounding the silica carrier.
  • the chemical bond (chemi cal attachment) is predominant, the viscosity of the reactant is lowered, and the alkylaluminoxane and the silica at high temperature are easy to diffuse to the pores of the silica.
  • the promoter component is supported by physical adsorption (physi cal adsorpt ion) on the silica surface. Therefore, according to the present invention, the apparent density and the catalytic activity of the polymer can be controlled not only by the alkylaluminoxane amount and the contact temperature, but also by the addition method.
  • the method of dividing the alkylaluminoxane at least twice or more at a high temperature and a low temperature is used.
  • Alkyl aluminoxane may be added twice, and the first reaction may be carried out in a line reaction in the range of the lowest temperature of 50t to the maximum temperature of 15CTC.
  • the alkyl aluminoxane is supported while being dividedly added to carry out the late reaction.
  • the alkyl aluminoxane is firstly supported by adding 50 to 90wt% of the total amount of the alkylaluminoxane in the first input, and the second supported by adding the remaining amount in the second input.
  • the alkyl aluminoxane which is the cocatalyst
  • the alumina is supported unevenly on the carrier, and aluminum is excessively present on the surface of the carrier.
  • metallocene compounds having small molecules are uniformly supported inside and outside. Therefore, the alkyl aluminoxane is added to the batch . Therefore, the metallocene compound supported therein is not activated, and thus, the total catalyst activity is reduced, and accordingly, polymerization by the catalyst activated only on the outside proceeds, resulting in low density.
  • alkyl aluminoxane (alkyl al iminoxane) is a cocatalyst component to assist the activity of the metallocene compound to be described later.
  • the step may be carried out by a method of reacting the carrier and the alkylaluminoxane by mixing and stirring in the presence or absence of a solvent.
  • the alkyl aluminoxane may be at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane and isobutyl aluminoxane.
  • the amount of the alkylaluminoxane supported on the silica carrier by the above step may be 5 to 15 dl / g based on the silica carrier lg. That is, within the supported amount range, by dividing at a high temperature and low temperature to support the alkyl aluminoxane on a silica carrier, the above-described shelf and post reaction of the alkyl aluminoxane can be performed.
  • a solvent may be used to induce a smooth contact reaction between the carrier and the alkylaluminoxane, or may be reacted without the solvent.
  • the solvent examples include aliphatic hydrocarbons such as nucleic acids, pentane and heptane; Aromatic hydrocarbons such as toluene and benzene; Hydrocarbons substituted with chlorine atoms such as dichloromethane; Most organic solvents such as ethers such as diethyl ether and tetrahydrofuran (THF); acetone and ethyl acetate can be used.
  • the solvent is a nucleic acid, heptane, Toluene or dichloromethane can be used.
  • the present invention can provide a silica carrier in which a larger amount of promoter (alkylaluminoxane) has penetrated into the silica carrier, and a significant amount of promoter (alkylaluminoxane) is bound to the outside thereof. It's fun.
  • the method for producing a supported metallocene catalyst according to the present invention includes the step of sequentially supporting at least one metallocene compound on the silica carrier on which the alkylaluminoxane is supported.
  • the catalyst is supported by sequentially supporting one or more metallocene catalysts on the silica carrier on which the alkylaluminoxane is supported, thereby interacting with the supported promoters according to the reaction conditions of the respective metallocene compounds.
  • the supported metallocene catalyst prepared in this manner can be confirmed by controlling the depth profile (depth prof i le) in the carrier of the catalyst using SEM / EDS analysis, thereby controlling the amount of alkylaluminoxane in the silica and the external loading.
  • the productivity of the polyolefin can be greatly improved.
  • the metallocene compound is a main catalyst component capable of exhibiting activity as a catalyst together with the aforementioned alkylaluminoxane.
  • the supported amount of the metallocene compound supported on the silica carrier by the above step may be 0.01 to 1 ⁇ ol / g based on the carrier lg. That is, in consideration of the contribution effect of the catalyst activity by the metallocene compound, it is preferable to fall within the above-described supporting amount range.
  • the temperature condition in the supporting step of the metallocene compound is not particularly limited.
  • the metallocene compound may be used one or more of the conventional ones in the technical field of the present invention without limitation.
  • the metallocene compound may include 1) a metallocene compound including a combination of non-bridged Cp and Cp, and 2) a combination of Si bridge Cp and Cp.
  • Metallocene compound comprising, 3) C Metallocene compound comprising a combination of bridge Cp (C br i dge Cp) and Cp system, 4) Metallocene compound containing a combination of Si bridge Cp (Si br i dge Cp) and amine system, 5) Ethylene Metallocene compound comprising a combination of bridge Cp (ethyl ene br i dge Cp) and Cp system, 6) Metallocene compound comprising a combination of phenylene bridge Cp and amine system, 7) Any metallocene compound including a CC, Si-C, or Si-Si bridge can be used.
  • the Cp may be cyclopentadienyl, indenyl, fluorenyl, indenoindole (Inln), or the like, and the structure thereof is not limited.
  • the Si-based bridge may include a t-subspecial-nuclear substituent and a similar structure thereof, and may include a tetrahydro-indene structure when the Si-based bridge includes an indene structure.
  • the metallocene compound of the present invention includes a low molecular metallocene compound (Cp-based) and a high molecular metallocene compound (for example, CGC type or ansa type).
  • the metallocene compound may be at least one selected from the group consisting of the following Chemical Formulas 1 to 6:
  • M 1 is a Group 4 transition metal
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, tetrahydro-1-indenyl, and fluorenyl radicals; One, they may be substituted with 1 to 20 carbon atoms;
  • R a and R b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 To alkenyl of C20, alkylaryl of C7 to C40, arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
  • Z 1 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 with arylalkoxy;
  • n 1 or 0;
  • M 2 is a Group 4 transition metal
  • Cp 3 and Cp 4 are the same or different from each other and ⁇ , which each independently cyclopentadienyl, inde selected from carbonyl, 4, 5, 6, 7-inde-tetrahydro-1-indenyl, and fluorenyl radicals group consisting of One, they may be substituted with hydrocarbons of 1 to 20 carbon atoms;
  • R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
  • ⁇ 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to the C40 alkylaryl, C7 to aryl C40 alkyl, C6 to aryl C20, a substituted or unsubstituted C1 to C20 of the alkylidene Or a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • ⁇ 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp3 ⁇ 4 c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 or Is a combination of;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which are substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
  • ⁇ Represents hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl Arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or Alkynyl of C2 to CIO;
  • Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
  • B 2 is a carbon Cp3 ⁇ 4 e for crosslinking the advert and J, germanium, silicon, phosphorous or nitrogen atom containing at least one of the radicals or a combination thereof;
  • J is any one selected from the group consisting of NR f , 0, PR f and S, wherein 1 is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl,
  • R10 to R13 and R10 'to R13' are the same or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 An arylalkyl group of C20 to C20, or an amine group of C1 to C20, and two or more adjacent ones of R10 to R13 and R10 1 to R13 1 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings.
  • Z1 and Z2 are the same as or different from each other, and each independently hydrogen, an alkyl group of C1 to C20, a cycloalkyl group of C3 to C20, an alkoxy group of C1 to C20, an aryl group of C6 to C20, an aryloxy group of C6 to C10, C2 to C20 alkenyl group, C7 to C40 alkylaryl group, or C7 to C40 arylalkyl group;
  • Q is C1 to C20 alkylene group, C3 to C20 cycloalkylene group, C6 to C20
  • X3 and X4 are the same as or different from each other, and each independently represents a halogen C1 ⁇
  • R 1 and R 2 are each independently hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, silyl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, and having 7 carbon atoms.
  • a metalloid of a Group 4 metal substituted with arylalkyl or hydrocarbyl of from 20 to 20; R 1 and R 2 or two R 2 may be connected to each other by an alkylidine including alkyl having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms to form a ring;
  • R 3 is independently hydrogen, halogen atom, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, 1-20 alkoxy, aryloxy or amino is also a carbon number of 6 to 20; wherein the R 3 in at least two R 3 are connected to each other may form an aliphatic ring or an aromatic ring;
  • CY 1 is a substituted or unsubstituted aliphatic or aromatic ring, and the substituents substituted in CY 1 are a halogen atom, alkyl having 1 to 20 carbon atoms, and having 2 to C carbon atoms. Alkenyl of 20, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, arylalkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, aryloxy of 6 to 20 carbon atoms, amido; When there are a plurality of substituents, two or more substituents in the substituents may be linked to each other to form an aliphatic or aromatic ring;
  • M is a Group 4 transition metal
  • Q 1 and Q 2 are each independently halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, and carbon atoms.
  • A is an alkyl group of hydrogen, halogen, C1 to C20, C2 to an alkenyl group of C20, C6 to C20 aryl group, C7 to an alkylaryl group of C20, C7 to alkoxy groups of C20 aryl groups, C1 to C20, C2 To a C20 alkoxyalkyl group.
  • Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;
  • M is a Group 4 transition metal
  • Xi and 3 ⁇ 4 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group C1 to C20 alkylsilyl group, C1 to C20 alkoxy group, or C1 to C20 Sulfonate groups;
  • Ci and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formulas 7a, 7b, or 7c, except that C1 and C2 are both Chemical Formulas 2c;
  • R1 to R17 and R1 'to R9' are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 malkenyl group, C1 to C20 alkyl Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group, Two or more adjacent to each other of R 10 to R 17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
  • the non-bridged Cp (non br i dge Cp) comprising a combination of Cp system
  • the metallocene compound may include a compound represented by Chemical Formula 1.
  • the metallocene compound including a combination of the Si bridge Cp (Si br idge Cp) and Cp-based and the metallocene compound including a combination of C-bridge Cp (C br idge Cp) and Cp-based,
  • the metallocene compound including a combination of the Si bridge Cp (Si br idge Cp) and an amine system may include a compound represented by Chemical Formula 3.
  • the metallocene compound including a combination of the ethylene bridge Cp and the Cp-based may include a compound represented by Chemical Formula 4.
  • hydrocarbyl as defined in Formula 5, is a monovalent group in a form in which hydrogen atoms are removed from hydrocarbons, and includes ethyl, phenyl, and the like.
  • the metalloid element comprises a look of "properties of the intermediate metal and the base metal to metalloid, arsenic, boron, silicon, tellurium or the like.
  • specific examples of the compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
  • specific examples of the compound represented by Chemical Formula 2 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
  • specific examples of the compound represented by Chemical Formula 3 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto ;
  • Q in Formula 4 is an alkylene group of C1 to C20
  • Z1 and Z2 are each independently hydrogen, an alkyl group of C1 to C20 or an alkoxy group of C1 to C20
  • X3 and X4 may be halogen, but are not limited thereto.
  • the compound represented by Chemical Formula 5 may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
  • Each R 7 is independently hydrogen or methyl; Q 5 and Q 6 are each independently Methyl, dimethylamido or chloride.
  • the ansa type compound may use a metallocene supported catalyst in which at least one metallocene compound represented by Chemical Formula 6 is supported on a carrier.
  • the metallocene compound represented by Chemical Formula 6 forms a structure in which an indeno indole derivative and / or a fluorene derivative are crosslinked by a bridge, and a non-covalent electron pair capable of acting as a Lewis base on the ligand structure. By having it, it can be supported on the surface having the Lewis acid characteristic of the carrier and can exhibit higher polymerization activity. In addition, it is possible to maintain high activity due to the high activity, including the electronically rich indeno indole group and / or fluorene group, due to the appropriate steric hindrance and the electronic effect of the ligand.
  • the alkyl group of C1 to C20 includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n—butyl group, tert'butyl group, pentyl group, nucleosil group, heptyl group, Octyl group etc. can be mentioned, It is not limited to this.
  • the alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.
  • the C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the C5 to C20 heteroaryl group includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group And triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.
  • alkoxy group for C1 to C20 examples include mesoxy group, ethoxy group, phenyloxy group, cyclonuxyloxy group, and the like, but are not limited thereto.
  • Group 4 transition metal examples include titanium, zirconium, hafnium, and the like, but are not limited thereto.
  • R1 to R17 and R1 'to R9' are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, and n-butyl.
  • tert-butyl group pentyl group, nucleosil group, heptyl group, octyl group, phenyl group, halogen trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, trimethylsilylmethyl group It is more preferably a methoxy group or an ethoxy group, but is not limited thereto.
  • L of Chemical Formula 6 is more preferably a straight or branched chain alkylene group of C4 to C8, but is not limited thereto.
  • the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.
  • a of Formula 6 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, mesoxymethyl group, tert-butoxy methyl group, 1-ethoxyethyl group, 1-methyl It is preferable that it is a 1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but it is not limited to this.
  • B of Formula 6 is silicon, but is not limited thereto.
  • a specific example of the structure represented by Chemical Formula 7a may include a structure represented by one of the following structural formulas, but is not limited thereto. -Si:
  • Chemical Formula 7b may include a structure represented by one of the following structural formulas, but is not limited thereto.
  • Chemical Formula 7c may include a structure represented by the following structural formulas, but is not limited thereto.
  • metallocene compound represented by Chemical Formula 6 include the following structural formula compounds, but are not limited thereto.
  • preparation method of the supported metallocene catalyst according to the present invention in addition to the above-described steps, may be carried out further including the steps that can be carried out conventionally in the art before or after each of the above steps.
  • the polymerization method of the present invention is not limited by the above-described steps.
  • one or more metallocene compounds when one or more metallocene compounds are used, one or more metallocene compounds may be sequentially supported on the silica carrier.
  • the present invention can further support a borate compound as a crab cocatalyst. That is, the present invention may further include a step of supporting a borate compound as a second cocatalyst on a silica carrier on which an alkylaluminoxane and at least one metallocene compound are supported.
  • the carrier is supported with an alkylaluminoxane as a first cocatalyst, a borate compound as a second cocatalyst, and one The above metallocene compound may be supported.
  • the second cocatalyst is included in the supported metallocene catalyst, the polymerization activity of the final prepared catalyst may be improved.
  • the borate-based compound as the second cocatalyst may include a borate-based compound in the form of a trisubstituted ammonium salt, a borate-based compound in the form of a dialkyl ammonium salt, or a borate-based compound in the form of a trisubstituted phosphonium salt.
  • Such a second catalyst include trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate, ⁇ , ⁇ -dimethylanilium tetraphenylborate , ⁇ , ⁇ ⁇ diethylanilium tetraphenylborate ,
  • Borate compounds in the form of trisubstituted ammonium salts such as tetrakis (2,3,4,6-tetrafluorophenyl) borate; Dioctadecyl Ammonium Borate compounds in the form of dialkylammonium salts such as tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclonucleoammonium tetrakis (pentafluorophenyl) borate; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate compounds in the form
  • the borate compound may be supported in an amount of 0.01 to 1 dl ol / g based on the silica carrier lg.
  • the supporting order is not particularly limited.
  • the borate-based compound may be finally supported on a silica carrier.
  • the present invention may optionally be carried out in the order of b) supporting an alkylaluminoxane on a silica carrier, supporting a borate compound, and then supporting one or more metallocene compounds.
  • a method for producing a polyolefin comprising the step of subjecting the olefinic monomers in the presence of the supported metallocene catalyst.
  • the supported metallocene catalyst according to the present invention can be used by itself in the polymerization reaction.
  • the supported metallocene catalyst may be prepared by using a prepolymerized catalyst by contact reaction with an olepin-based monomer.
  • the catalyst may be used separately, such as olefins such as ethylene, propylene, 1-butene, 1 ′ nucleene, 1-octene, and the like. It can also be prepared and used as a prepolymerized catalyst by contacting the monomers.
  • the supported metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms (for example, pentane, nucleic acid, heptane, nonane, decane and isomer thereof), aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane, It may be injected into the reactor by diluting with a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene. At this time, It is preferable to use after removing a small amount of water or air that can act as a catalyst poison by adding a small amount of alkylaluminum to the solvent.
  • an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms for example, pentane, nucleic acid, heptane, nonane, decane and isomer thereof
  • aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane
  • the polymerization reaction may be homopolymerized with one olefinic monomer or copolymerized with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
  • the polymerization of the olefin monomer may be carried out by reacting for about 1 to about 24 hours at a temperature of about 25 to about 500 ° C and about 1 to about 100 kgf / cm 2 .
  • the polymerization of the olefinic monomer may be carried out at a temperature of about 25 to about 500 ° C, preferably about 25 to about 200 ° C, more preferably about 50 to about 100 ° C.
  • the reaction pressure may also be carried out at about 1 to about 100 kgf / cni 2 , preferably about 1 to about 50 kgf / cm 2 , more preferably about 5 to about 40 kgf / cm 2 .
  • the olefin resin may be selected according to the type of poly olefins to be prepared, preferably ethylene, propylene, 1-butene, 1 kpentene, 4—methyl-1—pentene, 1-nuxene , 1 —Heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene 1-nuxadecene, 1-aitosen, norbornene, norbornadiene, ethylidene-norbornene, phenylnorbornene , Vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1-5-pentadiene, 1,6-nuxadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene
  • One or more selected olefinic monomers can be used.
  • the polyolefin produced according to the above method provides the effect of improving the walking density and the settling efficiency while maintaining high activity equal to or higher than the conventional one.
  • the polyolefin has a hanging density of 0.3 to 0.5 g / cin 3.
  • the polyolefin may also have a settling efficiency of 20 to 80%, which is defined by the following formula.
  • polyolefin using the supported metallocene catalyst of the present invention may exhibit a weight average molecular weight of 50,000 to 2 million.
  • preferred embodiments are provided to help understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto. . Comparative Examples 1 to 4 and Examples 1 to 11
  • Silica manufactured as a carrier, and it was calcined at 200 ° C. for 10 hours.
  • Toluene solution in which the metallocene compound (low molecular weight metallocene) is dissolved was added to the silica supported on methylaluminoxane, and stirred at 40 ° C. for 1 hour to react. Thereafter, a toluene solution in which the metallocene compound (polymer metallocene) was dissolved was added, and stirred at 40 ° C. for 1 hour for reaction (supporting amount of the metallocene compound: 0.2 Pa / g carrier). This was washed with a sufficient amount of toluene and dried in vacuo to obtain a supported metallocene catalyst as a solid powder.
  • the metallocene compound low molecular weight metallocene
  • a supported metallocene catalyst was further prepared by further supporting a second crude catalyst (borate compound).
  • the content was analyzed by using the FESEM SU-8020 system and EDS, and the pretreatment was observed after forming a cross section with a micro tom after molding the sample in epoxy.
  • Example 11 11 + 2 0.1 0.1 50.9 50.7
  • Cp derivatives bis (n-butylcyclopentadienyl) -zirconium dichloride (Bis (n-butylcyclopentadien yl) -zirconiumdi chloride)
  • the supported metallocene catalyst prepared in Examples 1 to 4 and the metallocene catalyst of the conventional general comparative example 1 were introduced into a loop slurry reactor, and polyethylene was prepared while continuously adding a gaseous ethylene monomer. At this time, the polyolefin which used the said comparative example 1 was made into the comparative example 5.
  • Comparative Example 5 using a conventional general supported catalyst was able to produce only polyethylene having a low apparent density (BD) and SE because of low catalytic activity.
  • Examples 10 to 12 of the present invention was able to produce a polyethylene polymer with improved polymer density while maintaining high active catalyst properties ⁇ + has been described in detail the specific part of the present invention in the art, For those of ordinary skill in the art, these specific descriptions are merely preferred embodiments, which limit the scope of the present invention. Is not clear . will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Cette invention concerne un procédé de préparation d'un catalyseur métallocène supporté très actif ayant une densité apparente élevée. Plus spécifiquement, cette invention concerne un procédé de préparation d'un catalyseur métallocène supporté constitué d'un ou de plusieurs types de composés métallocènes supportés sur un support en silice, le support en silice étant supporté par une quantité de co-catalyseur plus importante que dans un procédé classique qui pénètre à l'intérieur du support en silice, une quantité significative du co-catalyseur étant également combinée avec l'extérieur du support en silice. Le catalyseur selon l'invention peut servir à préparer un polymère de polyoléfine ayant une densité apparente de polymère et un rendement améliorés tout en conservant des propriétés de catalyseur très actives.
PCT/KR2014/011580 2013-11-28 2014-11-28 Procédé de préparation d'un catalyseur métallocène supporté WO2015080523A1 (fr)

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JP2016526289A JP6314223B2 (ja) 2013-11-28 2014-11-28 担持メタロセン触媒の製造方法
EP14865686.1A EP3050904B1 (fr) 2013-11-28 2014-11-28 Procédé de préparation d'un catalyseur métallocène supporté
CN201480064747.1A CN105980417B (zh) 2013-11-28 2014-11-28 负载型茂金属催化剂的制备方法
US15/033,866 US9657119B2 (en) 2013-11-28 2014-11-28 Preparation method of a supported metallocene catalyst

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