Method for the preparation of metallocene catalysts

专利摘要:
A method of preparing a supported metallocene catalyst is provided which introduces a metallocene and co-catalyst component onto a support. An alumoxane co-catalyst is introduced onto the support particles and a particulate catalyst support material is provided that contacts the dispersion of the metallocene catalyst in an aromatic hydrocarbon solvent. The metallocene solvent dispersion and alumoxane-containing support are mixed at a temperature of about 10 ° C. or less for a period of time sufficient for the metallocene to be reactively supported on the alumoxane support material. The supported catalyst is recovered from the aromatic solvent, optionally washed with an aromatic hydrocarbon, and subsequently washed with a paraffinic hydrocarbon solvent at a temperature of about 10 ° C. or less. The washed catalyst is dispersed in a viscous mineral oil having a viscosity substantially greater than that of the paraffinic hydrocarbon solvent.
公开号:KR20020066974A
申请号:KR1020020006561
申请日:2002-02-05
公开日:2002-08-21
发明作者:윌리엄제이. 가우시어；마가리토 로페즈；주니어.도날드지. 캠프벨
申请人:피나 테크놀러지, 인코포레이티드；
IPC主号:

专利说明:

Method for producing metallocene catalyst {METHOD FOR THE PREPARATION OF METALLOCENE CATALYSTS}
[1] The present invention relates to a supported metallocene catalyst system useful for the polymerization of ethylenically unsaturated compounds, and more particularly to a process for preparing a supported metallocene catalyst.
[2] Many catalyst systems used for the polymerization of ethylenically unsaturated monomers are based on metallocenes. Metallocenes are generally characterized by coordination compounds which introduce one or more cyclopentadienyl (Cp) groups (substituted or unsubstituted) coordinated with the transition metal via π bonds. Certain metallocene compounds form a highly active polymerization catalyst when combined with an activator or cocatalyst such as methylaluminoxane and optionally an alkylation / scavenging agent such as trialuminum compound. Various types of metallocenes are known in the art. For example, as described in US Pat. No. 5,324,800 to Welburn, such are monocyclic (single cyclopentadienyl groups), bicyclic (as shown in equation 1, two cyclopentadienes). Yl groups), or tricyclics (three cyclopentadienyl groups) coordinated with a central transition metal.
[3] Homogeneous or non-supported metallocene catalysts are known for their high catalytic activity, especially in olefin polymerizations. Under polymerization conditions in which the polymer is formed as solid particles, these homogeneous (soluble) catalysts form deposits of the polymer on the reactor walls and agitators, and the deposits prevent efficient heat exchange, require reactant cooling and move moving parts. They must be removed frequently because they cause excessive wear. In addition, solid particles formed from such homogeneous catalysts have undesirable particle forms with low bulk densities that make it difficult to circulate in the reaction, limiting the amount of work and difficult to transport out of the reactor. In order to solve these problems, several supported metallocene compounds have been proposed. As described in Welburn's patent, common supports include inorganic materials such as silica, alumina or polymeric materials such as polyethylene.
[4] Whether supported or not, metallocene compounds are stereoregular, causing polymerization of alpha olefins such as propylene to produce the most common crystallized stereoregular polymers, isotactic polypropylene and syndiotactic polypropylene. Can be characterized by a catalyst. In general, stereospecific metallocene catalysts have at least one chiral center and the ligand structure (generally cyclopentadienyl based) is limited conformally. Because of the fluidity of Cp-type ligands, it is common for at least one Cp ligand to be appropriately substituted to give several measurements of steric intensity. Such stereospecific metallocenes may comprise unbridged bicyclic compounds of the bicyclic batch of the general formula:
[5] (Cp) ₂ MeQn (1)
[6] This is characterized by isospecific metallocenes and dicyclopentadienyl of the general formula:
[7] CpCp'MeQn (2)
[8] This is characterized by the syndiospecific metallocenes described below. Wherein Me represents a transition metal and Cp and Cp 'represent a cyclopentadienyl group which may be unsubstituted or substituted with Cp' other than Cp, and Q represents an alkyl or other hydrocarbyl or halogen group (the most common 2 electron donor group), n is a number in the range of 1-3. In such instances, the steric intensity is via a group of substituents that cause a steric blockage between the two cyclopentadienyl molecular sieves, as described, for example, in US Pat. No. 5,243,002 to Razavi. Can be provided. Optionally, the cyclopentadienyl group is a constrained relationship provided by the structure bridged between the metallocene rings (not shown in formulas (1) and (2) above). Occasionally two cyclopentadienyl molecular sieves (either identical or different) benefit from the use of metallocene compounds covalently linked by so-called bridging groups such as dimethylsilylene groups. Bridging groups limit the rotation of two cyclopentadienyl molecular sieves and in most cases improve catalyst performance. Metallocenes containing such bridging groups are often referred to as stereorigids.
[9] In general, bridged metallocenes introduce two cyclopentadienyl groups (or substituted cyclopentadienyl groups), while bridged metals introduce a single cyclopentadienyl group bridged into a heteroatom aromatic group. Sendo is known in the art. For example, US Pat. No. 5,026,798 to Canich provides a dimethylsilyl-bridged cyclopentadienyl-anilino or cyclopentadienyl-group as well as a nitrogen atom of an anilino group. Describe other heteroatomic ligand structures with arrangements with transition metals. Other common bridging groups include CR ₁ R ₂ , CR ₁ R ₂ CR ₂ R ₃ , SiR ₁ R ₂ , and SiR ₁ R ₂ SiR ₁ R ₂ , wherein the R ₁ substituent is H or C ₁ -C ₂₀ hydrocarbyl It can be selected individually from radicals. Optional bridging groups may include nitrogen, phosphorus, boron or aluminum.
[10] In the above, isospecific and syndiospecific metallocene catalysts are useful in stereospecific polymerization of monomers. Stereospecific structural relationships of syndiotacticity and isotacticity may be involved in the formation of stereoregular polymers from various polymers. Stereospecific proparagation involves linear, branched or cyclic 1-dienes, such as 1,3-butadiene, vinyl aromatics, ie substituted vinyl compounds, such as styrene or vinyl chloride, alkyl vinyl ethers, i.e., isobutyl vinyl ethers. It may be applied to the polymerization of monomers unsaturated with C ₃ to C ₂₀ alpha olefin ethylene, which may be the same vinyl ether, or arylvinyl ether. Stereospecific polymer propagation is most evident in the production of polypropylene of isotactic or syndiotactic structure.
[11] The structure of isotactic polypropylene is described as having a methyl group attached to the third carbon atom of a continuous monomer unit falling on the same side of the imaginary plane through the main chain of the polymer, ie the methyl group above or below the plane. Oriented. The stereochemical order of isotactic polypropylene using Fisher's protruding formula is described by the formula:
[12]
[13] Each vertical segment in formula (3) represents a methyl group on the same phase of the polymer backbone. In the case of isotactic polypropylene, the majority of injected propylene units have the same relative arrangement with respect to their adjacent propylene units. Another way to describe the structure is through NMR. As above, Bovey's NMR nomenclature for the isotactic order is represented by each of the "m" s representing "meso" ... mmmm ..., a symmetric mirror between two adjacent monomer units. There are continuous pairs of methyl groups in the plane, or on the same plane of the polymer chain. As is known in the art, any deflection or shift in the structure of the chain lowers the degree of isotacticity and subsequently the degree of crystallinity of the polymer.
[14] In contrast to isotactic structures, syndiotactic propylene polymers are those in which the methyl group attached to the third carbon atom of the continuous monomer unit of the chain lies on an optional side of the polymer plane. In the case of syndiotactic polypropylene, the majority of injected propylene units have the opposite relative arrangement with respect to their adjacent monomer units. Syndiotactic polypropylene using Fischer protrusions can be represented by the racemic diamond with syndiotactic continuous ... rrrr ... as follows.
[15]
[16] As shown above, Bovey's NMR nomenclature for syndiotactic ordering is represented by each " r " representing a "racemic" diamond in which consecutive pairs of methyl groups are on the opposite side of the polymer chain plane. rrrr .... Similarly, any deflection or shift in the structure of the chain lowers the degree of syndiotacticity and subsequently crystallization of the polymer.
[17] In the working example the vertical segments represent methyl groups in the case of syndiotactic or isotactic polypropylene. In the case of poly 1-butene, the other terminating groups, ie the phenyl group in the case of chloride, polystyrene, etc. in the case of ethyl, polyvinyl chloride, etc., may be described equally in the same tendency as isotactic or syndiotactic. .
[18] The polypropylene resin is injected above or below the random arrangement of propylene units. Such materials are represented atactic and these polymers are determined by a common method of X-ray diffraction, heat of dissolution by differential scanning calorimeters, or density, which requires some sign of crystallization. Such atactic polymers tend to be more soluble in hydrocarbon solvents than polymers with multiple crystallizations. Syndiotactic with sufficiently high levels of syndiotactic and isotactic polymers with sufficiently high level isotacticity are semi-crystalline. Similarly, this can be accomplished by any technique known to those skilled in the art, such as XRD, DSC, or density measurement. It is common for the polymer to be obtained as a mixture of high stereoregular polymers and atactic polymers. In this example, it is useful to carry out solubility tests such as mass fraction lysates in xylene or hot heptane to confirm the amount of atactic polymer present. In most instances, the mass fraction melt of the hydrocarbon provides an indirect indication of the amount of atactic polymer present because the atactic polymer is easier to dissolve than the stereoregular control. While other stereoregular or quasi-stereoregular polymer structures, such as semiisotactic or stereoisoblock structures, are known, the main stereoregular polymer arrangements that are beneficial are preferably isotactic and syndiotactic polymers.
[19] Catalysts for producing isotactic polyolefins are described in US Pat. Nos. 4,794,096 and 4,975,403. These patents describe chiral, steric strength metallocene catalysts that polymerize olefins to form isotactic polymers and are particularly useful in the polymerization of high isotactic polypropylene. As described, for example, the stereoscopic strength of metallocene ligands in US Pat. No. 4,794,096 is imparted by means of structural bridges extending between cyclopentadienyl groups. In particular, the patent describes a stereoregular hafnium metallocene characterized by the following formula.
[20] R "(C ₅ (R ') ₄ ) ₂ HfQ _P (5)
[21] In formula (5), C ₅ (R ') ₄ is a cyclopentadienyl or substituted cyclopentadienyl group, R' is individually hydrogen or a hydrocarbyl radical having 1 to 20 carbon atoms and R '' Is a structural bridge that extends between cyclopentadienyl rings. Q is halogen or a hydrocarbon radical such as alkyl, aryl, alkenyl, alkylaryl or arylalkyl having 1 to 20 carbon atoms and p is 2.
[22] Catalysts for producing syndiotactic polypropylene or other syndiotactic polyolefins and methods of making such catalysts are disclosed in US Pat. No. 4,892,851 and Shamshoum at al, issued to Ewen at al. 5,807,800. In addition, these catalysts are bridged steric intensity metallocene catalysts, but in this case, the catalysts can be characterized in the following way with structural bridges extending between cyclopentadienyl groups that are not chemically similar.
[23] R "(CpR _n ) (CpR ' _m ) MeO _k (6)
[24] In formula (6), Cp represents a cyclopentadienyl or substituted cyclopentadienyl ring, and R and R 'represent a hydrocarbyl radical having 1 to 20 carbons. R ″ is a structural bridge between rings that impart steric strength to the catalyst. Me represents a transition metal and Q represents a hydrocarbyl radical or halogen. R ' _m is less than (CpR' _m ) than (CpR _n ). A steric other substituted cyclopentadienyl ring, wherein in formula (6) n varies from 0 to 4 (0 indicates no hydrocarbyl group, ie other substitutions other than bridging substituents on the cyclopentadienyl ring) M is 1-4, k is 0-3. Three different cyclopentadienyl rings produce syndiotactic polymers significantly more than isotactic polymers.
[25] Like such isospecific controls, syndiospecific metallocenes are used in combination with co-catalysts. One class of particularly useful co-catalysts is based on organoaluminum compounds that can take the formation of alumoxanes, such as methylalumoxane or modified alkylaluminoxane compounds. Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric aluminum oxygen compounds comprising chains intersecting aluminum and oxygen atoms, with aluminum transferring substituents, preferably alkyl groups. The exact structure of aluminoxanes is not known, but is generally general formula-(Al (R) -O-) _m for cyclic alumoxanes and RAl-O- (Al (R) -0) _m -AlR _{2 for} linear compounds. Where R is individually C ₁ -C ₁₀ hydrocarbyl, preferably alkyl, or halide, and m is an integer from 1 to about 50, preferably at least about 4. Generally, alumoxanes are reaction products of water and aluminum alkyls, and may include halides or alkoxide groups in addition to alkyl groups. For example, several other aluminum alkyl compounds such as trimethylaluminum and tri-isobutyl aluminum are reacted with water to produce the so-called modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxanes modified with minimal amounts of lower alkyl groups, such as methylalumoxane and isobutyl. Generally, alumoxanes comprise from a minimum amount sufficient to initiate aluminum alkyl isobutyl. Other cocatalysts include trialkylaluminum such as triethylaluminum (TEAl) or triisobutylaluminum (TiBAL) or mixtures thereof. In particular, methylaluminoxane and triethylaluminum (TEAl) are described in US Pat.
[26] Bridged metallocene ligands with dissimilar cyclopentadienyl groups are substituted cyclopenta, such as fluorene or substituted fluorene derivatives with 6,6-dimethyl pullbene to produce ligands characterized by isopropylidene bridge structure. Can result from the reaction of dienes. Preferably, this ligand structure is characterized by symmetry, as represented by isopropylidene (cyclopentadienyl fluorenyl) as shown in equation (9) of Patent 5,807,800. As described in Sam's Patent, '800, the bilateral symmetry of the ligand structure generally results in a balanced orientation for the broken line representing a plane of symmetry that extends through the bridge structure and the transition metal atoms.
[27] As described above, as described in US Pat. No. 5,324,800 to Welburn, the supported catalyst can be prepared by depositing a metallocene on a suitable catalyst support to convert the soluble metallocene into a release catalyst. Other supported catalysts are U.S. Pat.Nos. 4,701,432 and 4,808,561 to Welburn, U.S. Pat. 5,719,241, and Patent No. 5,807,700 to Samsoum.
[28] As described in patent '432 to Welburn, the support may be any support, such as talc, inorganic oxides, or resinous support materials such as polyolefins. Specific inorganic oxides include silica and alumina used alone or in combination with other inorganic oxides such as magnesia, titania, zirconia and the like. Non-metallocene transition metal compounds, such as titanium tetrachloride, can be introduced as supported catalyst components. The inorganic oxide used as the support has an average particle size in the range of 30 to 600 microns, preferably in the range of 30 to 100 microns, 50 to 1000 m ² / g, preferably a surface area of 100 to 400 m ² / g, 0.5 to 3.5 cc / g Preferably, having a pore volume of about 0.5 to 2 cc / g. In general, particle size, surface area, pore volume, and number of surface hydroxy groups are not critical in the Wellburn procedure. In particular, a catalyst in which bis (cyclopentadienyl) zirconium dichloride (unbridged metallocene) is supported on high surface area silica dehydrated under dry nitrogen at 600 ° C. is described in Wellburn's patent and Davidson's patent. In 952, properties are described. Welburn's patent '561 describes a release catalyst formed by reacting metallocene and alumoxane with a support material. In Welburn's patent '561 the support is described similarly to the support of patent' 432. Various other catalyst systems related to supported metallocene catalysts are described in US Pat. No. 5,308,811 to Sugar and 5,444,134 to Matsumoto. In both patents, the supports are characterized by a variety of high surface area inorganic oxide or clay-based materials. In Sugar's patent, the support materials are characterized such as clay minerals, ion-exchange layered compounds, diatomaceous earth, silicates, or zeolites. As described in Sugar's patent, high surface area support materials should have a pore volume having a radius of at least 20 Angstroms. In particular, clare and claire minerals such as montmorillonite are described as preferred in Sugar's patent. Sugar's patented catalyst component mixes support materials such as triethylaluminum, trimethylaluminum, various alkylaluminum chlorides, alkoxides or hybrids, metallocenes, and organoaluminum compounds, or alumoxanes such as methylalumoxane, ethylalumoxane, etc. It is manufactured by. The three components can be mixed together in any order or they can be contacted simultaneously. The patent granted to Matsumoto is that the support has SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₂ , CaO, ZnO, BaO, ThO ₂ and silica alumina, zeolite, ferrite ferrite, and inorganic oxide carriers such as glass fibers and mixtures thereof. Other carriers include MgCl ₂ , Mg (O-Et) ₂ , and polymers such as polystyrene, polyethylene, polypropylene, substituted polystyrene and polyarylate, starch, and carbon. The moving bodies have a surface area of 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, a pore volume of 0.1 to 5 cm ³ / g, preferably 0.3 to 3 cm ³ / g, and a particle size of 20 to 100 microns. Have
[29] In various inorganic oxides used as supports, one or other forms of silica are widely described as support materials for metallocene catalysts. The patent 5,719,241 to Rajavi, which describes a wide range of organic oxide and resinous support materials, identifies silica having a surface area of between about 200 and 600 m ² / g as a preferred support. In particular, the support identified above is described in '952 to Grace, having a surface area of 322 m ² / g. In the preparation of supported metallocenes as described in Rajavi's patent, silica is dried in vacuo for 3 hours to remove water and then suspended in toluene and reacted with methylalumoxane for 3 hours at reflux temperature. Two metallocene solutions are added to the silica and the mixture is stirred for one hour followed by three washes with toluene to remove unreacted alumoxane. The supernatant is removed and the solid support containing metallocene is washed with toluene and dried in vacuo. In addition, the silica characterized by Davidson D-948 or Davidson D-952 appears as a conventional metallocene support. For example, US Pat. No. 5,466,649 to Jejelowo describes the use of Davidson D-948 silica dehydrated as a support for various unbridged metallocenes used with supported co-catalysts. do. Patent 5,498,581 to Welch describes silica for use as a support for bridged or unbridged metallocenes treated with carbon monosides, water and hydroxy groups. In particular, Davidson D-948, silica, having an average particle size of 50 microns is described. Other silica-based supports are described in US Pat. No. 5,281,679 to Zegeluo, 5,238,892 to Chang, and 5,399,636 to Alk. The Chang and Zegeluo patent describes the use of the silica support identified as Davidson D-948 and is characterized by amorphous silica gel containing about 9.7 wt.% Water. As described in the Chang and Zegeluo patents, alumoxane is deposited on the surface of the silica gel by a direct reaction of non-dehydrated silica gel with alkyl aluminum to ensure the amount of conversion of alkyl aluminum to alumoxane with a high degree of oligomerization. It is formed directly. Water absorbed gels have a surface area in the range of 10-700 m ² / g, a pore volume of about 0.5-3 cc / g, and about 10-50% by weight for the Zegeluo patent and about 6-20% by weight for the window patent. It is characteristic to have an absorbed water content. The average particle size for silica is from 0.3 to 100 microns in the window patent and from 10 to 100 microns in the Zegeluo patent. After the alumoxane silica gel component is formed, the metallocene can be added to the wet slurry. Another supported catalyst system is described in European Patent Application No. 96111719.9 (EPO 819706A1) to Samsoum. As described above, the silica support is pretreated with an alumoxane, such as methylalumoxane, with the addition of syndiospecific metallocene on the MAO-treated silica. Supported metallocenes include organo-aluminum co-catalysts such as monoalkyl or dialkyl aluminum halides as described above, including trialkylaluminum such as trimethylaluminum, triethylaluminum or tri-isobutyl aluminum (TIBAL) Used with In the supported catalysts described in EPO819706, the silica support is a small pore size silica that is slurried in a high surface area, dried, non-polar solvent and contacted with methylalumoxane in the solvent. Metallocenes are dissolved in non-polar solvents and are the same as those used as solvents, especially for alumoxanes. Solid metallocene supported on alumoxane-treated silica is recovered from the solvent, dried and introduced into a transfer liquid such as mineral oil. The Samsoum EPA application also describes a pre-polymerization step that can be used to reduce the aging time of the catalyst in trialkyl aluminum or other aluminum co-catalysts.
[30] Other supported catalyst systems incorporating bridged metallocene catalysts are described in US Pat. No. 5,968,864 to Samsoum. Catalytic efficiency is improved by a preparation procedure in which a support such as silica is treated with alumoxane in a non-polar solvent such as toluene and contacted with a solution of metallocene at a reduced temperature, preferably in the temperature range of 0-20 ° C. The resulting solid is washed with hexanes and dried overnight at room temperature.
[31] Summary of the Invention
[32] According to the present invention, metallocene and co-catalyst components can alleviate or eliminate problems with reactor contamination and undesirable polymer fragments, while being able to separate and store mineral oil slurries used in the production of stereoregular polymers. A method of making a supported metallocene catalyst is provided that can be tailored to a support that provides a supported catalyst system. The resulting supported catalyst provides excellent activity that can be maintained when the process is used to produce isospecific or syndiospecific supported catalysts.
[33] In carrying out the invention, an alumoxane co-catalyst is provided with a particulate catalyst support material introduced into the support particles. The support material is associated with the dispersion of the metallocene catalyst in the aromatic hydrocarbon solvent. The metallocene solvent dispersion and alumoxane-containing support are mixed at a temperature of about 10 ° C. or less for a sufficient period of time for the metallocene to be reactively supported on the alumoxane-support material. Depending on the mixing time, which can vary from a few minutes to several hours, the supported catalyst is recovered from the aromatic solvent and optionally washed with an aromatic hydrocarbon, followed by a paraffinic hydrocarbon solvent to remove a substantial amount of the aromatic solvent from the sequentially supported catalyst. It is washed with. This cleaning procedure is performed at low temperatures of about 10 ° C. or less. Thereafter, the washed catalyst is dispersed in a viscous mineral oil having a viscosity substantially greater than that of the paraffinic hydrocarbon solvent. Generally, mineral oils have a viscosity of at least 65 centistokes as measured by ASTM D445 at 40 ° C. This may be contrasted with the viscosity of paraffinic hydrocarbon solvents which are generally up to 2, preferably up to 1 centipoise, at reduced temperature conditions. The step of drying the washed catalyst is not necessary and generally the washed catalyst at the time of dispersion contains a significant amount of paraffinic hydrocarbon solvent and a small amount of aromatic hydrocarbon solvent. Preferably, after the supported catalyst is recovered from the aromatic solvent and before being washed with the paraffinic hydrocarbon solvent, further washing steps are performed with the aromatic solvent to remove unsupported metallocene from the supported catalyst.
[34] In another aspect of the invention there is provided a particulate catalyst support which is particulate silica having a particle size in the range of 10-100 microns and silica having an elliptical arrangement in an average particle size in the range of about 10-60 microns, preferably in the range of 10-15 microns. do. Generally, the silica is dried at elevated temperatures for a period of time to moderately dehydrate the silica. Higher temperatures can be used, but mild heat treatment, often on the order of 100-160 ° C, is sufficient. The particulate support material is contacted with the alumoxane co-catalyst in the aromatic transfer liquid. The mixture of support, carrier and alumoxane cocatalyst is heated at elevated temperature for a time to allow alumoxane to immobilize on the particulate support. For example, the mixture may be heated under reflux conditions of about 100 ° C. for one to several hours. The mixture is cooled and the alumoxane-containing support is separated from the transfer liquid. The alumoxane-containing support material is washed with an aromatic hydrocarbon solvent to remove substantially no alumoxane (or aluminum alkyl residues) that are not supported or free of excess alumoxane (or aluminum alkyl residues) to immobilize the support. The alumoxane-containing support material is cooled to a reduced temperature of about 10 ° C. or less and the dispersion of the metallocene in an aromatic solvent is a temperature of about 10 ° C. or less such that the metallocene is reactively supported on the alumoxane-containing support material. In the mixture as described above. The supported catalyst is recovered and washed with a low viscosity paraffinic hydrocarbon solvent at a reduced temperature below about 10 ° C. as described above and dispersed in a viscous mineral oil. Optionally, the catalyst is washed with mineral oil and no paraffin hydrocarbon solvent is used. Polyolefin catalysts prepared in this tendency have good performances such as high activity.
[35] Detailed description of the invention
[36] The present invention relates to a process for the preparation of supported metallocenes which is generally carried out under low temperature conditions in the deposition of metallocene catalysts on alumoxane-containing supports, wherein the supported metallocenes obtained once are directly transferred to mineral oil transfer. Dispersed in phase. Such supported catalysts are suitable for use in the polymerization of ethylene, propylene, and higher olefins, such as in the preparation of ethylene / propylene copolymers including homopolymerization of olefins or their polymerization. This procedure is in contrast to the procedure of the prior art, as described in the above patent granted to Welburn, which generally ignores the order of addition of metallocene and alumoxane under room temperature conditions, and the final catalyst particles remove volatiles. Dry for an extended period of time. Similarly, in the procedure where the alumoxane, described in Rajabi patent '241, is first added and mixed with the support at reflux temperature, the finally supported catalyst is dried under vacuum. In contrast to the procedure of the prior art, the present invention proceeds once the alumoxane is immobilized on the support to carry out the metallocene support reaction under a low temperature, generally in the range of about −20 ° C. to 10 ° C., to proceed to wash the catalyst with hydrocarbons. And dissolve the washed catalyst with viscous mineral oil without interfering drying steps. The cleaning and dispersion of the catalyst with mineral oil is carried out under atmospheric temperature conditions.
[37] The supported catalyst produced according to the present invention provides several important properties. Metallocene loading and alumoxane loading on the support material can be controlled to a predetermined level. This is particularly evident for certain silica supports that are preferred for use in the present invention, and it is desirable to control the alumina / silica ratio to a level that may depend on the properties of the metallocene component. In particular, in the case of stereospecific metallocenes, the alumoxane / silica ratio is final for defects that often appear as "fish eyes" in metallocene activity, polymer fragments, contamination, and finished products produced from olefin polymers during polymerization. Controlled to reach a predetermined ratio for efficient features of the catalyst. Furthermore, for metallocenes and support materials other than preferred stereospecific metallocenes and silica supports, the present invention is directed to the loading of metallocenes on alumoxane containing supports as generally practiced in the prior art at relatively low temperatures. Likewise, this can be done with direct dispersion of the catalyst supported by a viscous mineral oil dispersion without interfering drying steps. In general, the resulting catalyst system has a very small loss in activity, ie higher activity with a long “stock life” during storage, especially before the catalyst is stored at low temperature.
[38] The catalyst was treated with triisobutylaluminum (TIBAL) and in accordance with an aging procedure as described in Ed and Samsoum's US Application No. 09 / 086,080, filed May 28, 1998, "Process for the Syndiotactic Propagation of Olefins." Aging with the same alkylaluminum compound enhances the activity. In brief, the enhanced activity of the catalyst can be achieved by aging the organoaluminum compound, in particular the metallocene supported in TIBAL, in mineral oil overnight (about 12 hours) or in another cycle, ie for one or two days according to the following procedure. Can be. Detailed aging procedures are directed to contacting the same portion of metallocene and the same portion of TIBAL in the mineral oil slurry to maintain it at room temperature at 25 ° C. overnight (about 12 hours) before polymerization. A general master batch of syndiospecific or isospecific catalysts is prepared from a slurry of 180 mg of supported metallocene (metallocene and support), 8.3 ml of mineral oil, 180 mg of TIBAL at a concentration of 25% by weight in hexane Can be. After an overnight aging procedure, 0.1 ml of the master slurry is used for each propylene polymerization. For further explanation of the aging procedure, the above-mentioned US Patent Application No. 09 / 086,080 is incorporated herein by reference. In the above, the present invention provides a method for loading metallocene catalyst precursor onto an alumoxane-containing support material by sequential dispersion in a mineral oil transfer liquid, as well as alumoxane on a support material, in particular to be applicable to a particular silica support. It provides a preferred procedure for loading. However, while the invention is particularly preferred for the use of silica supports, it may also be carried out with other support materials, as described, for example, in Patent No. 5,719,241 to Rajavi, which may be used with polyethylene or polypropylene. Same polyolefins, polystyrenes, and inorganic oxides other than alumina, magnesia, titania and other inorganic oxides. Talc, such as described in Rajavi's patent, clay and clay minerals, such as described in Sugar's above patent, may also be used as support materials. Zeolites and glass fibers may also be used as well as Fe ₂ O ₃ , B ₂ O ₂ , CaO, ZnO, BaO, ThO ₂ , MgCO ² , and Mg (O-Et) ₂ described in the above Matsumoto patent. Other inorganic oxides may also be used in the present invention, in general they are less preferred than preferred silica supports. Support materials that can be used to carry out the invention are described in Rajavi's patent 5,719,241, Sugar's patent 5,308,811, and Matsumoto's patent 5,444,134 and incorporated herein by reference. One suitable type of silica support used in the present invention includes silica particles having an average size in the range of about 10 to 100 microns and includes silica particles that function to support alumoxane on its outer surface. Specifically, particulate silica having an elliptical arrangement and an average particle size in the range of about 10-60 microns is included in the silica support. One such support is available from Asahi Glass Company, Ltd., designated H-121. Such silica supports are naturally ellipsoidal and have an average particle size of about 12 microns and a pore volume of about 0.9 ml / g. As described below, alumoxane is primarily immobilized on the outer surface of the elliptical silica particles. The average particle size of the silica is substantially enhanced to a value of about 0.5 micron or more after addition of alumoxane on the support using the protocol of the present invention, after which the alumoxane is refluxed in a solvent and incorporated on the support particles, then cooled and washed do. In addition, it is common for MAO / supports to form aggregated species with an average particle size substantially larger than the initial support.
[39] The metallocenes used in the present invention include metallocene compounds known to be useful in olefin polymerization procedures and are monocyclic, bicyclic, or tricyclic, as described in Welburn's patent 5,324,800 and Rajabi's patent 5,719,241. Click olefins. However, in particular the invention is applicable to the preparation of supported metallocenes based on stereospecific metallocenes, in particular isospecific and syndiospecific metallocenes. As described below, other variables for alumoxane loading and metallocene content are applicable for forming isospecific and syndiospecific supported metallocenes, and the present invention is readily applicable to alumoxanes in a relatively narrow range. And close control of metallocene loading.
[40] Preferred strength metallocenes for use in the present invention are characterized by metallocenes which introduce a ligand structure with at least one suitable substituent on at least one cyclopentadienyl ring disposed as a central transition metal. At least one cyclopentadienyl ring is substituted and provides an orientation with respect to the transition metal that is stericly different from the orientation of the other cyclopentadienyl group. Thus, two groups of cyclopentadienyl are in another relationship that provides steric intensities for transition metal atoms arranged to substantially prevent rotation of the ring structure. Stereoscopically dissimilar ring structures may be chemically identical in the case of certain isospecific metallocenes or chemically different in the case of syndiospecific metallocenes. However, if two chemically identical cyclopentadienyl groups are associated with the ligand structure, they should be stericly different for the racemic bis (indenyl) structure and for the transition metal for the meso bis (indenyl) ligand structure. Should be the same in three dimensions.
[41] Bridged isospecific metallocenes can be characterized as chiral steric intensity metallocenes defined by the following formula.
[42] R "(C _p (R ') ₄ ) ₂ MeQ _p (7)
[43] Wherein (C _p (R ′) ₄ ) is a substituted cyclopentadienyl ring; Each R 'is the same or different and is a hydrogen or hydrocarbyl radical having 1 to 20 carbon atoms; R ″ is a structural bridge between the two (C _p (R ') ₄ ) which impart steric strength to the catalyst with two (C _p (R') ₄ ) rings in the racemic arrangement relating to Me R ″ is a substituted or unsubstituted alkenyl radical having 1 to 4 carbon atoms, silicon hydrocarbyl radical, germanium hydrocarbyl radical, phosphorus hydrocarbyl radical, nitrogen hydrocarbyl radical, boron hydrocarbyl radical, and aluminum hydrocarbyl radical Is selected from the group consisting of; Me is a 4b, 5b, or 6b metal on the periodic table; Each Q is a hydrocarbyl radical or halogen having 1 to 20 carbon atoms; p has a range of 0-3.
[44] Particularly preferred kinds of isospecific metallocenes are based on racemic bis (indenyl) ligand constructs. Indenyl groups may be substituted or unsubstituted and may include saturated indenyl groups such as aromatic or indenyl groups as well as substituted or unsubstituted tetrahydroindenyl groups. Detailed examples of isospecific metallocenes suitable for use in the present invention include racemic-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride, racemic-dimethylsilyl bis (2-methyl-indenyl ) Zirconium dichloride, racemic-dimethylsilyl bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, racemic-isopropylidene bis (2,3-dimethylcyclopentadienyl) zirconium dimethyl, la Semi-isopropylidene bis (2,4-dimethyl-cyclopentadienyl) zirconium dimethyl, ethylene bis (indenyl) zirconium dimethyl, and corresponding dichlorides. Other metallocenes include ethylene bis (2-methyl indenyl) zirconium dichloride, diphenyl silyl bis (2-methyl indenyl) zirconium dichloride, diphenyl silyl bis (2-methyl, 4-phenyl-indenyl) zirconium Dichloride, and diethyl silyl bis (2-methyl, 4--phenyl indenyl) zirconium dichloride.
[45] Bridged syndiospecific metallocenes are characterized by metallocenes showing bilateral symmetry and are defined by the formula:
[46] R "(Cp _a R _n ) (Cp _b R ' _m ) MeQ _p (8)
[47] Wherein Cp _a is a substituted cyclopentadienyl ring and Cp _b is an unsubstituted or substituted cyclopentadienyl ring; Each R is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms; Each R _m ′ is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms; R ″ is a structural bridge between cyclopentadienyl groups that impart steric strength to the catalyst and is substituted or unsubstituted alkenyl radical, silicon hydrocarbyl radical, germanium hydrocarbyl radical, phosphorus hydro having 1 to 4 carbon atoms Selected from the group consisting of carbyl radicals, nitrogen hydrocarbyl radicals, boron hydrocarbyl radicals, and aluminum hydrocarbyl radicals; Me is a 4b, 5b, or 6b metal on the periodic table; each Q is 1-20 carbon atoms gateun the hydrocarbyl or halogen; 0≥p≥3; 0≥m≥4; 1≥n≥4; R 'm is (Cp _b R' _m) is (Cp _a R _n) and selected to be different ring Bridged syndiospecific metallocenes that may be used in the present invention are diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (fluore). Neil) Zirco A mixture of dichloride and isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isobutylidene (cyclopentadienyl-1-fluorenyl) zirconium dimethyl , Isopentylidene (cyclopentadienyl-1-fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium dimethyl, diphenyl methylene (cyclopentadienyl-1-flu Orenyl) zirconium dimethyl, and the corresponding dichloride or methylchloride.
[48] As described by reference in US Pat. No. 5,807,800, the bilateral symmetry of bridged metallocene ligand structures generally appears in a balanced orientation with respect to broken lines representing a plane of symmetry that extends through the bridge structure and transition metal atoms. Left and right symmetry is useful to illustrate metallocene structures useful in the present invention. In addition, other metallocene compounds that lack symmetry can be used while the stereoscopic environment for the metal is such that the two placement sites on the transition metal have opposite isomeric selectivity. To illustrate this part, consider MePhC-cyclopentadienyl fluorenyl zirconium dichloride. This metallocene lacks symmetry due to the advantages of asymmetric bridges and is suitable for use in the present invention. Similarly, Me ₂ C (2-Me-Cp) (Flu) ZrCl ₂ produces syndiospecific catalysts despite lack of left and right symmetry. A key requirement of the transition metal catalyst precursor is that the reaction site has the opposite isomer selectivity towards olefin insertion. Apparently this may appear as follows. Opposite isomer selectivity of the metallocene catalyst precursor to metal is R ₂ and R ₃ is a group R ₆ and R in three dimensions greater than or less than ₇ Anti-R ₆ and R ₇ is established as an array of sterically large metal than the group R ₂ and R ₃ do. In the case of Me ₂ CpFluZrCl ₂ , R ₂ and R ₃ are hydrogen atoms and R ₆ and R ₇ are clearly larger hydrocarbyl radicals than hydrogen.
[49]
[50] In general, in the metallocenes used in the present invention, Me is titanium, zirconium, hafnium or vanadium; Preferably, Q is methyl or halogen, more preferably chlorine, and in general, k is 2 but can vary by the valence of the metal atom. Exemplary hydrocarbyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, acyl, cetyl, phenyl and the like. Other hydrocarbyl radicals include other alkyl, aryl, alkenyl, alkylaryl, or arylalkyl radicals. For metallocenes in which the oxidation state is not appropriate during use or storage (eg, group 5-based metallocenes), it is often necessary to use halogenated materials such as carbon tetrachloride, chloroform, etc. to maintain good catalytic performance. useful.
[51] While other loading factors are preferred for syndiospecific and isospecific catalysts, the same general procedure for loading alumoxane on a support material first and then loading metallocene is the same for both isospecific and syndiospecific metals. Applicable to other metallocenes as well as rosene. In general, the present invention does not pay attention to particular metallocenes and can be described with respect to silica supports. Silica is dried to remove significant water content. The drying procedure can be carried out under nitrogen or vacuum overnight (about 12 hours) at a temperature of about 100-160 ° C. The silica should be dried at a temperature at which the weight loss upon ignition at 300 ° C. (LOI) is at most 4%, preferably at most 2%, and most preferably in the range of 0.1-1.5% by weight. The dried silica is slurried in toluene or other similar aromatic hydrocarbon solvent. Although alumoxane and other alumoxanes can be used in toluene, preferably methylalumoxane (MAO) is added to the silica / toluene mixture, and the silica and MAO are mixed together so that the resulting slurry has a temperature of about 100 ° C. or more. Heated for several hours. For example, where toluene is used as the aromatic solvent, the MAO silica / toluene mixture may be heated at the reflux temperature of toluene at 115 ° C. for about 4 hours. The resulting product, with the MAO immobilized on the support, cooled to room temperature of about 25 ° C. over several hours and allowed the particulate silica supported with MAO to precipitate in solution without mixing or other agitation. The liquid is poured off and washed with toluene several times to filter out particulate material and remove excess alumoxane or other aluminum compounds that are not immobilized on the support. Generally, two to four washes of toluene at room temperature are used in this step.
[52] At this temperature, the alumoxane-containing support is mixed with cooled toluene up to about 10 ° C. In general, in these and sequential steps the temperature is in the range of 0-10 ° C. In practice, lower temperatures may be used, but are sometimes unnecessary. At this temperature, again at reduced temperatures, the metallocene dispersed in toluene or other aromatic solvents is stirred for a time for the MAO / silica slurry and metallocene to react reactively on the support material with alumoxane Is added to the mixture. Although some significant reaction of the metallocene with the support occurs initially for several minutes, it is desirable to maintain the mixing of the support and the metallocene for at least one hour. The mixing time can be up to several hours if desired.
[53] At the conclusion of the support reaction, the solid material is filtered out of the liquid and washed with a low temperature toluene solution, generally 0-10 ° C., again several times with a paraffinic hydrocarbon solvent such as hexane at temperatures below about 10 ° C. Three sequential hexane washes may be performed to reduce the amount of toluene on the support material substantially to several percent or less. In this step, low temperature mineral oil is added to the supported catalyst of the filtrate to form a dispersion of the catalyst in the mineral oil. As described above, because there is no need for an interference drying step, the resulting dispersion of mineral oil contains a minimum amount of hexane or other paraffinic solvent and toluene or a smaller amount of other aromatic solvent. However, the drying step can be applied immediately before the addition of mineral oil. The mineral oil, when used in the polymerization reaction, should have sufficient viscosity to maintain the supported catalyst with gentle stirring in the dispersed suspension. Of course, mineral oils have a substantially greater viscosity than the viscosity of paraffin hydrocarbyl solvents. In general, at 10 ° C., the paraffinic hydrocarbon solvent has a viscosity of about 2 centistokes or less, while at 10 ° C., the paraffin mineral oil is about 10 centistokes or more. The final liquid dispersant comprises a less volatile paraffinic solvent and a much smaller amount of aromatic solvent used to rinse the supported catalyst with toluene. In general, the minimum components indicated above are present in about 5-15% by weight mineral oil, 1-13% by 5 hexanes or up to 2% by weight other paraffin solvents or other aromatic solvents.
[54] Optionally the oil can be evaporated to remove residual hexane and toluene. As indicated above, the present invention can be used to introduce alumoxane co-catalysts and metallocenes into a wide variety of supports. Features of many catalyst supports, such as those described above, are the outer shell in which alumoxane is initially deposited on the support surface, the metallocene forms an intermediate shell around which the alumoxane surrounds the support particles, and the metallocene covers the alumoxane. It is applied to alumoxane to provide an arrangement to form the Treatment with toluene or other solvents subsequent to the alumoxane support reaction, together with the associated metallocenes applied later, removes excess alumoxane that is not immobilized on the support so as not to be released from the support during the polymerization reaction.
[55] Similar ideas apply for sequentially-applied metallocenes. In the above, the metallocene is formed of the metallocene supported as the outer shell surrounding the organoaluminum co-catalyst in the case of the surface support as described below. Excess metallocene is removed during the polymerization reaction with the contaminated product in the polymerization reactor. By initial cold washing with toluene or other aromatic solvent on the newly supported catalyst, excess metallocene is removed to produce a final product where substantially all metallocene is immobilized on the support. In order to avoid any adsorption of the metallocene by residual toluene, sequential low temperature washing with hexane or other hydrocarbons removes a large advantage in metallocene adsorption.
[56] In the above, the present invention is applicable to silica supports having an average particle size in the range of about 10 to 100 microns in which the organoaluminum compound and the metallocene are supported on the outer surface of the support particles. Such support particles generally comprise a small particle sized silica support having an elliptical arrangement and having an average particle size in the range of 10-15 microns, specifically about 12 microns. Other silica supports on which alumoxane and metallocene are primarily supported on the surface are silica supports in which the silica particles are amorphous or granular and may be characterized by larger average particle sizes of about 10-100 microns. In addition to the silica support H-121 identified above, such silica particles were assigned to the Fuji Silisa Chemical Company, designated G10 with a pore volume of about 0.7 mm / g and an elliptical arrangement Q10 as opposed to G6, an irregular granular arrangement, Silica available from Fuji Silysa Chemical Company, Ltd.
[57] As described below, in a preferred embodiment, the relative amount of alumoxane on the support is present in 1 part by weight of the support material as 0.5-1.5 parts by weight of alumoxane in the starting reaction mixture, but the amount is specific to the support and isospecific or Diospecific metallocenes can vary in a range depending on whether they are relevant or not. More specifically, for such metallocenes, the weight ratio of alumoxane to silica support material ranges from 0.7 to 1.0. Metallocene loadings generally vary from about 0.6 to 6 weight percent of MAO / support material.
[58] In addition to syndiospecific or isospecific metallocenes, several substantial improvements are observed to result from the practice of the present invention over the general prior art procedures described above. The catalytic activity is substantially higher for both isospecific and syndiospecific metallocenes, and is approximately doubled compared to the activity of catalysts prepared according to prior art practice. The syndiospecific and isospecific catalysts shown increase in activity when the TIBAL aging procedure is performed. The polymer product produced by the catalyst formed according to the invention is increased in the range of about 15-20% for higher bulk densities, generally isospecific metallocenes. For example, for both isospecific and syndiospecific catalysts, the shelf-life of the catalyst dispersed in mineral oil without the conventional interference drying step is much greater than that produced by conventional techniques. Improved stock-life can be characterized by an increase of three months or more over several weeks of shelf life for catalysts produced by conventional techniques.
[59] Experimental work on the present invention is carried out using bridged isospecific and syndiospecific catalysts. Isospecific catalyst is racemic-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride. To exemplify the present invention using a syndiospecific catalyst, the following metallocenes, diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, are used. To illustrate that the present invention is useful for the production of a wide molecular weight distribution resin, the catalyst is 1.6 wt% diphenylmethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and 0.4 wt% isopropylidene (Cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride. These isospecific and syndiotactic metallocenes are supported on MAO / silica using the process of the invention and are also supported according to standard techniques performed at temperatures above room temperature and the catalyst content dried according to conventional procedures. . In general, supported isospecific catalysts prepared by standard techniques are in terms of grams of polymer per gram of catalyst per 3,000 to 6,000 hours relative to the activity of catalysts prepared according to the invention in the range of about 8,000 to 13,500 g / g / h. / g / h). The bulk density of polymers produced from prior art catalysts ranges from about 0.3 to 0.36 g / ml, while the bulk density of polymers produced from catalysts of the present invention ranges from about 0.35 to .04 g / ml. In addition, in the present invention, the shelf life is increased from two weeks to more than 12 weeks. Finally, the catalyst produced according to the invention can be stored as a non-naturally flammable slurry in contrast to the spontaneously flammable solids produced in the prior art.
[60] Provided are methods of preparing supported metallocene catalysts that introduce metallocene and co-catalyst components onto a support. The alumoxane co-catalyst is introduced onto the support particles to provide a particulate catalyst support material in contact with the dispersion of the metallocene catalyst in the aromatic hydrocarbon solvent.
[61] The following examples illustrate the practice of the present invention.
[62] General Procedure for Unaged Syndiotactic Polypropylene (sPP) Polymerization
[63] The polymerization is carried out in a 4L Autoclave Engineers' Zipperclave reactor equipped with a Magnetdrive pitched-blade impeller operating at 800 rpm. The reactor is covered to maintain the polymerization temperature within 1 ° C. of 60 ° C. fixed temperature. The dry and de-oxygen reactor is charged with 750 g of liquid propylene and 41.2 mmol of hydrogen at room temperature (25 ° C.). The catalyst / oil slurry (containing 36 mg catalyst) is added to a stainless steel cylinder filled with 109 mg triisobutylaluminum. The catalyst / cocatalyst is precontacted for about 3 minutes and further 750 g of propylene aliquot is added to the reactor. Heat the reactor to 60 ° C. for 3 minutes and run for 60 minutes. The reactor contents are rapidly volatilized and the polymer is dried overnight in a vented place.
[64] General Procedure for Aged sPP Polymerization
[65] The same procedure as described above is used except the catalyst (144 mg) and TIBAL (144 mg) were precontacted in a 20 mL Weton glass bottle for 12 hours. Aliquots of aged catalyst (36 mg) are combined with 72 mg TIBAL and added to the reactor containing liquid propylene as described above. The precontact time between catalyst and aliquots of additional TIBAL is about 3 minutes.
[66] General Procedure for Unaged Isotactic Polypropylene (miPP) Polymerization
[67] The polymerization is carried out in a 4L Autoclave Engineers' Zipperclave reactor equipped with a Magnetdrive pitched-blade impeller operating at 800 rpm. The reactor is covered to maintain the polymerization temperature within 1 ° C. of 67 ° C. fixed temperature. The dry and de-oxygen reactor is charged with 750 g of liquid propylene and 10 mmole of hydrogen at room temperature (25 ° C.). Catalyst / oil slurry (containing 36 mg catalyst) is added to a stainless steel cylinder filled with 72 mg triethylaluminum. The catalyst / cocatalyst is precontacted for about 3 minutes and further 750 g of propylene aliquot is added to the reactor. Heat the reactor to 67 ° C. for 3 minutes and run for 60 minutes. The reactor contents are rapidly volatilized and the polymer is dried overnight in a vented place.
[68] General Procedure for Aged miPP Polymerization
[69] The same procedure as described above is used except the catalyst (144 mg) and TIBAL (144 mg) were precontacted in a 20 mL Weton glass bottle for 12 hours. An aliquot of aged catalyst (36 mg) is combined with 36 mg of TEAL and added to the reactor containing liquid propylene as described above. The precontact time between catalyst and aliquots of additional TIBAL is about 3 minutes. The rest of the procedure is as above.
[70] Bulk Density Determination
[71] Bulk density measurement is performed by weighing the contents of the 100 ml graduated cylinder containing the polymer powder without filling.
[72] Melt Flow Index Measurement
[73] The polymer melt flow is recorded on a Tinius-Olsen Extrusion platometer at 2.16 Kg mass at 230 ° C. The polymer powder is stabilized with about 1 mg of 2,6-ditert-butyl-4-methylphenol (BHT).
[74] Preparation of Methylaluminoxane-Supported Silica
[75] Silica gel (160 g, Asahi Glass Sunsphere H-121C) is dried in an oven at 150 ° C. for 62 hours. The weight loss due to heat of the dried silica is recorded using a thermogravimetric analyzer. Weight loss at 150, 300 and 900 ° C. was observed to be 0.97%, 1.13% and 5.49%, respectively. 20 g of dried silica is placed in a 1 liter, three necked round bottom flask in a glove box with a condenser attached. To this is added 200 mL of dry deoxygenated toluene. The slurry is gently stirred and 64 ml of 30% MAO by weight of toluene are added. The flask is sealed and removed from the glove box and attached to the Schlenk branch under mild nitrogen pressure. The reaction mixture is heated to 115 ° C. and refluxed for 4 h using a magnetic stirrer. The slurry is cooled at room temperature. Toluene supernatant is removed via cannulae and the wet product is sequentially washed twice with 200 mL toluene and three times with 200 mL dry deoxygenated hexane. MAO on silica is dried in vacuo to yield a white solid. Drying MAO on silica in this example provides the convenience of experimental evaporation of other catalysts.
[76] Comparative Example 1. Preparation of sPP Catalyst
[77] 3 g of MAO on H121C silica is added to a 100 mL round bottom flask containing 30 mL of toluene and the flask is cooled to 0 ° C. Diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (45 mg) is slurried with 10 mL toluene in a 20 mL Weton glass bottle. Metallocene slurry is added to the stirred MAO solution on silica. Conversion of the metallocene is completed with a second 10 mL toluene. Metallocene and MAO / silica are reacted at 0 ° C. for 1.5 hours. If the solids do not go away, the supernatant is removed via a cannula. The wet supported catalyst is washed once with 50 mL toluene and the solids are removed again through the cannula. Subsequently, the wet supported catalyst is washed with 30, 50 mL hexanes. After pouring the hexane supernatant three times, the catalyst slurry is dried in vacuo. 2.6 g of dry supported sPP catalyst remain.
[78] Comparative Example 2. Preparation of sPP Catalyst
[79] 5 g of MAO on H121C silica is added to a 100 mL round bottom flask containing 30 mL of toluene and the flask is cooled to 0 ° C. Diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (80 mg) and isopropylidene (cyclopentadienyl) (2,7-bis tert -butylfluorenyl) -zirconium dichloride (20 mg ) Is slurried with 10 mL toluene in a 20 mL Weton vial. Metallocene slurry is added to the stirred MAO solution on silica. Conversion of the metallocene is completed with a second 10 mL toluene. Metallocene and MAO / silica are reacted at 0 ° C. for 1.5 hours. If the solids do not go away, the supernatant is removed via a cannula. The wet supported catalyst is washed once with 50 mL toluene and the solids are allowed to settle down and removed via cannula. Subsequently, the wet supported catalyst is washed with 30, 50 mL hexanes. After pouring the hexane supernatant three times, the catalyst slurry is dried in vacuo. 4.6 g of dry supported sPP catalyst remain.
[80] Example 1: Preparation of sPP Catalyst
[81] 5 g of MAO on H121C silica is added to a 100 mL round bottom flask containing 30 mL of toluene and the flask is cooled to 0 ° C. Diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (80 mg) and isopropylidene (cyclopetadienyl) (2,7-bis tert -butylfluorenyl) -zirconium dichloride (20 mg ) Is slurried with 10 mL toluene in a 20 mL Weton vial. Metallocene slurry is added to the stirred MAO solution on silica. Conversion of the metallocene is completed with a second 10 mL toluene. Metallocene and MAO / silica are reacted at 0 ° C. for 2 hours. If the solids do not go away, the supernatant is removed via a cannula. The wet supported catalyst is washed once with 50 mL toluene and the solids are allowed to settle down and removed via cannula. Subsequently, the wet supported catalyst is washed with 30 ° C., 50 mL hexane at 0 ° C. After pouring hexane supernatant three times, the wet catalyst slurry is diluted with 45 g of mineral oil. SPP supported catalyst remains with a solid slurry of 7.2%.
[82] Example 2: Preparation of sPP Catalyst
[83] 5 g of MAO on H121C silica is added to a 100 mL round bottom flask containing 30 mL of toluene and the flask is cooled to 0 ° C. Diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (100 mg) is slurried with 10 mL toluene in a 20 mL Weton glass bottle. The metallocene slurry is added to the stirred MAO solution on silica. The conversion of metallocene is completed with two 10 mL toluene. Metallocene and MAO / silica are reacted at 0 ° C. for 1.5 hours. If the solids do not go away, the supernatant is removed via a cannula. The wet supported catalyst is washed once with 50 mL toluene at 0 ° C. and the solids are allowed to settle down and removed via cannula. Subsequently, the wet supported catalyst is washed with 30, 50 mL hexanes. After pouring the hexane supernatant three times, the catalyst slurry is dried slightly in vacuo and slurried in mineral oil (45 g) to produce 9.0% solid slurry.
[84] Comparative Example 3: Preparation of a miPP Catalyst
[85] 5 g of MAO on H121C silica is added to a 100 mL round bottom flask containing 25 mL of toluene at room temperature. Racemic dimethylsilylene bis (2-methyl-4-phenyl-indenyl) zirconium dichloride (92 mg) is slurried with 15 mL toluene in a 20 mL Weton glass bottle. Metallocene slurry is added to the stirred MAO solution on silica. Metallocene and MAO / silica are reacted at room temperature for 1 hour. If the solids do not go away, the supernatant is removed via a cannula. Subsequently, the wet supported catalyst is washed with 30, 50 mL hexanes. After pouring the hexane supernatant three times, the catalyst slurry is slightly dried in vacuo. 5 g of dry supported miPP catalyst remain.
[86] Example 3: Preparation of miPP Catalyst
[87] 5 g of MAO on H121C silica is added to a 100 mL round bottom flask containing 25 mL of toluene at room temperature. Racemic dimethylsilylene bis (2-methyl-4-phenyl-indenyl) zirconium dichloride (92 mg) is slurried with 15 mL toluene in a 20 mL Weton glass bottle. The metallocene slurry is added to the stirred MAO solution on silica at 0 ° C. Metallocene and MAO / silica are reacted at 0 ° C. for 2 hours. If the solids do not go away, the supernatant is removed via a cannula. Subsequently, the wet supported catalyst is washed with 30, 50 mL hexane at 0 ° C. After pouring the hexane supernatant three times, 48 g of mineral oil is added to the wet catalyst slurry to produce 7.3% final solids.
[88] Example 4: Preparation of miPP Catalyst
[89] 10 g of MAO on H121C silica is added to a 250 mL round bottom flask containing 75 mL of toluene at room temperature. Racemic dimethylsilylene bis (2-methyl-4-phenyl-indenyl) zirconium dichloride (184 mg) is slurried with 25 mL toluene in a 600 mL Weton glass bottle. The metallocene slurry is added to the stirred MAO solution on silica at 0 ° C. Metallocene and MAO / silica are reacted at 0 ° C. for 1 hour. If the solids do not go away, the supernatant is removed via a cannula. Subsequently, the wet supported catalyst is washed with 30, 50 mL hexanes. After pouring hexane supernatant three times, 100 g of mineral oil is added to the wet catalyst slurry. The oil slurried catalyst is evaporated for 45 minutes to remove most of the volatile components to yield 7.3% final solids. This example illustrates that an optional evaporation step can be used for the preferred procedure.
[90] The polymerization results are summarized in Table 1. The first column in Table 1 shows the catalyst used in the polymerization with reference to the above control example or comparative example indicated by "CE" and the example indicated by "E" in Example 1. The second column indicates whether the aging procedure described above in TIBAL has been used. The third column shows the activity of the catalyst in grams of propylene per gram of catalyst per hour and the fourth column shows the bulk density in grams per cubic centimeter of polymer production. The fifth column shows the melt flow rate and the sixth column shows the xylene melt content (XS) of the polymer product. The seventh column shows the melting temperature of the polymer product. The eighth column shows that the molecular weight is thousands, and the last column shows the molecular weight distribution (D) as M _w -M _n expressed by weight average molecular weight, M _w and number average molecular weight, M _n . The procedure invented here results in a substantial increase in catalytic activity (see, eg, Example 1 and Comparative Example 1). The improvement is evident when the catalyst is aged with aluminum alkyl for an extended time period.
[91] One23456789 catalystAging (TIBAL)Activity (g / g / hr)BD (g / cc)MF (g / 10 min)XS (%)T _m (℃)M _w / 1000D (M _w / M _n ) CE Example 1no11,2000.391.41.4128.01982.3 Example 1no13,5000.331.7---- CE Example 2no14,8000.385.42.9130.31344.1 Example 2no13,0000.408.44.2130.51184.0 CE Example 3no6,5000.364.0---- Example 3no10,0000.373.1---- Example 4no10,6000.383.8---- CE Example 1Yes14,9000.371.51.6127.31742.6 Example 1Yes24,0000.351.2---- CE Example 2Yes15,6000.357.03.8129.31274.1 Example 2Yes25,0000.417.35.2130.51194.4 Example 4Yes11,1000.400.61----
[92] Examples 1 and 2, and Comparative Examples 1 and 2 were tested under standard sPP polymerization conditions. Examples 3 and 4, and Comparative Examples 3 and 4 were tested under standard miPP polymerization conditions.
[93] It is to be understood that changes and modifications of the invention can be made without departing from the spirit and scope of the invention as defined by the appended claims.

权利要求:
Claims (34)
[1" claim-type="Currently amended] In a supported method for preparing a metallocene catalyst,
(a) providing a particulate catalyst support material comprising support particles having an alumoxane co-catalyst introduced on the support particles;
(b) providing a dispersion of metallocene in an aromatic hydrocarbon solvent;
(c) mixing the metallocene with the alumoxane containing the support at a temperature of about 10 ° C. or less for a period of time sufficient to be reactively supported on the alumoxane support material;
(d) recovering the supported catalyst from the aromatic solvent;
(e) washing the supported catalyst with a paraffinic hydrocarbon solvent at a temperature of about 10 ° C. or less; And
(f) dispersing the washed catalyst with a viscous mineral oil having a viscosity greater than that of the paraffinic hydrocarbon solvent.
How to include.
[2" claim-type="Currently amended] The method of claim 1 wherein the catalyst washed at the time of dispersion in the viscous mineral oil comprises a residual amount of the paraffinic hydrocarbon solvent.
[3" claim-type="Currently amended] 3. The method of claim 2, wherein the cleaning of the support catalyst with the paraffinic hydrocarbon solvent is effective in that the support catalyst reduces the residual aromatic solvent on the supported catalyst to a value of 50 wt% or less of the supported catalyst. How to.
[4" claim-type="Currently amended] The method of claim 1 wherein the viscous mineral oil has a viscosity of at least about 10 centistokes.
[5" claim-type="Currently amended] 5. The method of claim 4 wherein the paraffinic hydrocarbon solvent has a viscosity of 2 centistokes or less.
[6" claim-type="Currently amended] 2. The process of claim 1, wherein the supported metallocene catalyst is subsequently washed with an aromatic solvent to recover unsupported metallocene from the supported metallocene catalyst in step (d) prior to step (e). cleaning the supported catalyst according to (e).
[7" claim-type="Currently amended] The method of claim 1 wherein the support material comprises silica-alumoxane particles having an average particle size in the range of 10-50 microns.
[8" claim-type="Currently amended] 8. The metallocene catalyst of claim 7, wherein the metallocene catalyst is a stereospecific metallocene catalyst for introducing a metallocene ligand structure having two stericly indeterminate cyclopentadienyl ring structures disposed as central transition metal atoms; At least one of the cyclopentadienyl ring structures is a substituted cyclopentadienyl which provides an orientation for the transition metal atom that is stericly different from the orientation of other cyclopentadienyl groups with respect to the transition metal atom and the cyclopenta Wherein both dienyl groups provide steric stiffness relationship with each other to the batch transition metal atoms to prevent rotation of the ring structure.
[9" claim-type="Currently amended] According to claim 8, wherein the stereospecific metallocene is of the formula
R "(Cp _a R _n ) (Cp _n R ' _m ) MeQ _p
And a syndiospecific metallocene.
Wherein Cp _a is a substituted cyclopentadienyl ring and Cp _b is an unsubstituted or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms Each R _m 'is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms; R "is a structural bridge between cyclopentadienyl groups that impart steric strength to the catalyst and is 1 to 4 carbon atoms Me is selected from the group consisting of substituted or unsubstituted alkenyl radicals, silicone hydrocarbyl radicals, germanium hydrocarbyl radicals, phosphorus hydrocarbyl radicals, nitrogen hydrocarbyl radicals, boron hydrocarbyl radicals, and aluminum hydrocarbyl radicals; A 4b, 5b, or 6b group metal on the periodic table; each Q is a hydrocarbyl having 1 to 20 carbon atoms or Halogen; 0≥p≥3; 0≥m≥4; 1≥n≥4; R 'm is (Cp _b R' is selected to be sterically different, and _m) a (Cp _a R _n)).
[10" claim-type="Currently amended] 10. The method of claim 9, wherein R is selected to form a substituted or unsubstituted fluorenyl group with (Cp _a R _n ).
[11" claim-type="Currently amended] The method of claim 10, wherein Me is titanium, zirconium, hafnium, or vanadium.
[12" claim-type="Currently amended] 12. The process of claim 11, wherein R " is methylene, ethylene, organosylsilyl, substituted methylene or substituted ethylene radicals.
[13" claim-type="Currently amended] 13. The compound of claim 12, wherein R is selected such that (Cp _a R _n ) forms a substituted or unsubstituted fluorenyl radical having bilateral symmetry, and R 'is (Cp _b R' _m ) having bilateral symmetry. And an alkyl substituted or unsubstituted cyclopentadienyl radical.
[14" claim-type="Currently amended] The method of claim 13, wherein the weight ratio of the alumoxane to the silica is in the range of about 0.5-1.5.
[15" claim-type="Currently amended] The method of claim 14, wherein R ″ (Cp _a R _n ) (Cp _b R ′ _m ) is isopropylidene (cyclopentadienyl-1-2,7-di-tert-butyl fluorenyl) ligand or diphenyl A methylene (cyclopentadienyl-1-fluorenyl) ligand is formed.
[16" claim-type="Currently amended] The method of claim 1, wherein the catalyst support material comprises particulate silica having an elliptical arrangement for introducing the alumoxane co-catalyst and an average particle size in the range of 10-60 microns.
[17" claim-type="Currently amended] 17. The method of claim 16, wherein the alumoxane co-catalyst is introduced significantly into the silica particles on the surface.
[18" claim-type="Currently amended] The method of claim 8, wherein the stereospecific metallocene is of the formula:
R "(C ₅ (R ') ₄ ) ₂ MeQ _p
Isospecific three-dimensional strength metallocene.
Wherein (C _p (R ′) ₄ ) is a substituted cyclopentadienyl ring; each R ′ is a hydrogen or hydrocarbyl radical having the same or different and having 1 to 20 carbon atoms; Is a structural bridge between two (C _p (R ') ₄ ) conferring stereoscopic strength to the catalyst having two (C _p (R') ₄ ) rings in the relevant racemic arrangement; Selected from the group consisting of substituted or unsubstituted alkenyl radicals having 4 to 4 carbon atoms, silicon hydrocarbyl radicals, germanium hydrocarbyl radicals, phosphorus hydrocarbyl radicals, nitrogen hydrocarbyl radicals, boron hydrocarbyl radicals, and aluminum hydrocarbyl radicals Me is a 4b, 5b, or 6b group metal on the periodic table; each Q is a hydrocarbyl radical or halogen having 1 to 20 carbon atoms; 0 ≦ p ≦ 3)
[19" claim-type="Currently amended] 19. The method of claim 18, wherein Me is titanium, zirconium, hafnium or vanadium.
[20" claim-type="Currently amended] 20. The method of claim 19, wherein R " is methylene, ethylene, organosylsilyl, substituted methylene, or substituted ethylene radicals.
[21" claim-type="Currently amended] 19. The method of claim 18, wherein the weight ratio of the alumoxane to the particulate silica support is in the range of about 0.5 to 1.5.
[22" claim-type="Currently amended] The method of claim 18, wherein the (C ₅ (R ′) ₄ ) group is a substituted or unsubstituted indenyl group.
[23" claim-type="Currently amended] 23. The method of claim 22, wherein the indenyl groups are each substituted at adjacent positions.
[24" claim-type="Currently amended] The method of claim 23, wherein the isospecific metallocene is selected from racemic dimethylsilyl (2-methyl-4-phenyl indenyl) ₂ zirconium dichloride, racemic dimethylsilyl (2-methyl indenyl) ₂ zirconium dichloride, And racemic dimethylsilyl (2-methyl-2,5-benzo indenyl) ₂ zirconium dichloride and mixtures thereof.
[25" claim-type="Currently amended] In the process for producing a supported metallocene catalyst,
(a) providing a particulate catalyst support material;
(b) contacting said particulate support material with an alumoxane co-catalyst in an aromatic transfer liquid;
(c) heating said mixture of support, transfer liquid and alumoxane co-catalyst at elevated temperature for a period sufficient to immobilize said alumoxane on said particulate support;
(d) cooling the mixture and separating the alumoxane-containing support material from the transfer liquid;
(e) washing the alumoxane containing the support material with an aromatic solvent to remove excess alumoxane;
(f) cooling the alumoxane containing the support material to a reduced temperature of about 10 ° C. or less and at the reduced temperature dispersing a metallocene of an aromatic solvent in the support material;
(g) metallocene on the support material with the alumoxane to provide the metallocene, aromatic solvent, and support material with the metallocene supported metallocene catalyst at a reduced temperature of about 10 ° C. or less. Mixing for a time supported reactively to;
(h) recovering the resulting supported metallocene catalyst from the aromatic solvent;
(i) washing the supported catalyst with a paraffinic hydrocarbon solvent at a reduced temperature of about 10 ° C. or less; And
(j) dispersing the supported metallocene in a viscous mineral oil having a viscosity substantially greater than that of the paraffinic hydrocarbon solvent.
Method comprising a.
[26" claim-type="Currently amended] 26. The method according to claim 25, wherein before the step (i) sequential to step (h), the hydrogenated water, the supported metallocene catalyst is washed with an aromatic solvent to remove unsupported metallocene from the supported metallocene catalyst, Washing the catalyst supported according to step (i).
[27" claim-type="Currently amended] 26. The system of claim 25, wherein the metallocene catalyst is a stereospecific metallocene catalyst that introduces a metallocene ligand structure having two stericly dissimilar cyclopentadienyl ring structures disposed as central transition metal atoms; At least one of the cyclopentadienyl ring structures is a substituted cyclopentadienyl which provides an orientation for the transition metal atom that is stericly different from the orientation of other cyclopentadienyl groups with respect to the transition metal atom and the cyclopenta Wherein both dienyl groups provide steric stiffness relationship with each other to the batch transition metal atoms to prevent rotation of the ring structure.
[28" claim-type="Currently amended] 27. The process of claim 25, wherein the catalyst support material in step (a) is particulate silica having an elliptical arrangement and an average particle size in the range of 10-15 microns.
[29" claim-type="Currently amended] 29. The method of claim 28, wherein the particle size of the elliptical particulate silica is increased to a value of at least 5 microns after addition of the alumoxane on the support material.
[30" claim-type="Currently amended] 26. The method of claim 25, wherein the alumoxane co-catalyst is significantly introduced onto the silica particles on its surface.
[31" claim-type="Currently amended] The method of claim 25, wherein the stereospecific metallocene is of the formula:
R "(Cp _a R _n ) (Cp _b R ' _m ) MeQ _p
And a syndiospecific metallocene.
Wherein Cp _a is a substituted cyclopentadienyl ring and Cp _b is an unsubstituted or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms Each R _m 'is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms; R "is a structural bridge between cyclopentadienyl groups that impart steric strength to the catalyst and is 1 to 4 carbon atoms Me is selected from the group consisting of substituted or unsubstituted alkenyl radicals, silicone hydrocarbyl radicals, germanium hydrocarbyl radicals, phosphorus hydrocarbyl radicals, nitrogen hydrocarbyl radicals, boron hydrocarbyl radicals, and aluminum hydrocarbyl radicals; A 4b, 5b, or 6b group metal on the periodic table; each Q is a hydrocarbyl having 1 to 20 carbon atoms or Halogen; 0≥p≥3; 0≥m≥4; 1≥n≥4; R 'm is (Cp _b R' is selected to be sterically different, and _m) a (Cp _a R _n)).
[32" claim-type="Currently amended] 30. The method of claim 29, wherein the weight ratio of said alumoxane to silica is in the range of about 0.7 to 1.0.
[33" claim-type="Currently amended] The method of claim 27, wherein the stereospecific metallocene is of the formula:
R "(C ₅ (R ') ₄ ) ₂ MeQ _p
Isospecific three-dimensional strength metallocene.
Wherein (C ₅ (R ′) ₄ ) is a substituted cyclopentadienyl ring; each R ′ is the same or different and is a hydrogen or hydrocarbyl radical having 1 to 20 carbon atoms; Is a structural bridge between two (C ₅ (R ') ₄ ) conferring steric strength to the catalyst having two (C ₅ (R') ₄ ) rings in the relevant racemic arrangement; Selected from the group consisting of substituted or unsubstituted alkenyl radicals having 4 to 4 carbon atoms, silicon hydrocarbyl radicals, germanium hydrocarbyl radicals, phosphorus hydrocarbyl radicals, nitrogen hydrocarbyl radicals, boron hydrocarbyl radicals, and aluminum hydrocarbyl radicals Me is a 4b, 5b, or 6b group metal on the periodic table; each Q is a hydrocarbyl radical or halogen having 1 to 20 carbon atoms; 0 ≦ p ≦ 3)
[34" claim-type="Currently amended] 34. The method of claim 33, wherein the weight ratio of the alumoxane to the particulate silica support is in the range of about 0.7 to 1.0.

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同族专利:

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公开号 | 公开日

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US20020137623A1|2002-09-26|

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EP1231225A1|2002-08-14|

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KR100874132B1|2008-12-15|

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AT504609T|2011-04-15|

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TWI235161B|2005-07-01|

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DE60239650D1|2011-05-19|

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CN1370785A|2002-09-25|

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JP2002275207A|2002-09-25|

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EP1231225B1|2011-04-06|

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CN1231499C|2005-12-14|

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US6777367B2|2004-08-17|

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JP4239136B2|2009-03-18|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-02-13|Priority to US09/782,753

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2001-02-13|Priority to US09/782,753

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2002-02-05|Application filed by 피나 테크놀러지, 인코포레이티드

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2002-08-21|Publication of KR20020066974A

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2008-12-15|Application granted

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2008-12-15|Publication of KR100874132B1

优先权:

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申请号 | 申请日 | 专利标题

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US09/782,753|2001-02-13|

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US09/782,753|US6777367B2|2001-02-13|2001-02-13|Method for the preparation of metallocene catalysts|