Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • 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
  • C08F4/65927—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 bridged
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• the present invention relates to a mixed catalyst useful in a process for polymerizing one or more olefm(s).
• the mixed catalysts are bulky ligand transition metal metallocene-type catalyst compounds where at least one catalyst is a bridged, bulky ligand metallocene-type compound, and at least one catalyst is a bridged, asymmetrically substituted, bulky ligand metallocene-type compound.
• Polymers produced using the mixed catalyst of the invention are easier to process into end-use applications such as films or molded articles.
• Typical bulky ligand transition metal metallocene-type compounds are generally described as containing one or more ligands capable of ⁇ -5 bonding to the transition metal atom, usually, cyclopentadienyl derived ligands or moieties, in combination with a transition metal selected from Group 4, 5 or 6 or from the lanthanide and actinide series of the Periodic Table of Elements. Exemplary of the development of these and other metallocene-type catalyst compounds and catalyst systems are described in U.S. Patent Nos. 5,017,714, 5,055,438, 5,096, 867, 5,198,401, 5,229,478, 5,264,405, 5,278,119, 5,324,800,
• Linear polyethylenes known as Linear Low Density Polyethylene (LLDPE) made with traditional Ziegler-Natta catalysts, are more difficult to process than high pressure produced low density polyethylenes (LDPE) because linear polyethylenes exhibit a higher viscosity at a higher shear region which requires more motor power, produces higher extruder pressure and prone to melt fracture at the extrusion rates of LDPE' s.
• LLDPE Linear Low Density Polyethylene
• Linear polyethylenes also have poor bubble stability compared to LDPE due to a lower melt viscosity at low shear rates and/or lower melt strength. On the other hand, however, linear polyethylenes exhibit superior physical properties as compared to LDPE's. In order to take advantage of the superior physical and mechanical properties of linear polyethylenes, expensive antioxidants and processing aids are added to the polymer, and extrusion equipment must be modified to achieve commercial extrusion rates.
• a second technique to improve the processability of linear polyethylenes is to broaden the molecular weight distribution by blending two or more linear polyethylenes with significantly different molecular weights, or by changing to a polymerization catalyst that produces a polymer having a broad molecular weight distribution.
• U.S. Patent No. 4,530,914 discusses a catalyst system for producing polyethylene having a broad molecular weight distribution using two different metallocene-type catalyst compounds having different propagation and termination rate constants for ethylene polymerization.
• U.S. Patent No. 4,937,299 is directed to a homogeneous catalyst system of at least two metallocene-type catalyst compounds each having different reactivity ratios for use in a single reactor to produce a polymer blend.
• U.S. Patent No. 5,470,811 discusses producing polymers having improved product properties using an isomeric mixture of two or more substituted metallocene-type catalyst compounds.
• EP-A2-0 743 327 discuss the use of meso and racemic bridged mixed metallocene-type catalysts compounds to produce ethylene polymers having improved processability.
• U.S. Patent No. 5,516,848 relates to a process for producing polypropylene using a bridged mono-cyclopentadienyl heteroatom containing compound and an unbridged, bis-cyclopentadienyl containing compound.
• EP-B1-0 310 734 discusses the use of a mixed bridged bulky ligand hafnium and zirconium metallocene-type catalyst compounds to produce a polymer having broad molecular weight distribution.
• 5,696,045 describes using at least two different bridged, bulky ligand zirconium metallocene-type catalyst compounds to produce propylene polymers having a broad molecular weight distribution where one of the stereorigid zirconocenes has as a bulky ligand, an indenyl ligand having a substituent on the six-member ring.
• EP-B1-516 018 describes using two different bridged bulky ligand zirconium metallocene-type catalyst compounds to produce a broad molecular weight distribution polypropylene polymer where one of the bridged metallocenes has as the bulky ligands, indenyl ligands, that are substituted in at least the two position.
• the resulting polymer from a series polymerization process is a combination or blend of two different polymers.
• These polymer blends typically, contain a high molecular weight and a low molecular weight component.
• U.S. Patent No. 5,665,818 discusses using two fluidized gas phase reactors in series using a transition metal based catalyst to form an in situ polymer blend having improved extrudability.
• EP-B1-0 527 221 discusses a series reactor process using metallocene-type catalyst systems for producing bimodal molecular weight distribution polymer products.
• series or multistage reactor processes are expensive and more difficult to operate.
• This invention provides for a mixed bridged metallocene-type catalyst compounds of at least two different such catalyst compounds, at least one having bridged bulky ligands and the other having bridged bulky ligands that are asymmetrically substituted.
• the mixed bridged metallocene-type compounds of the invention together with an activator form a catalyst system useful in a polymerization process for producing polymers having improved processability.
• the bridged, bulky ligand metallocene-type compounds of the invention are different from the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compounds of the invention.
• the invention relates to a process for polymerizing olefm(s) in the presence of at least two different catalyst compounds, one being a bridged, bulky ligand transition metal metallocene- type catalyst compound and the other being a bridged, asymmetrically substituted, bulky ligand transition metal metallocene-type catalyst compound.
• the invention provides for a method for making a supported mixed catalyst of at least two different catalyst compounds, where a bridged, bulky ligand transition metal metallocene-type catalyst compound is combined with a bridged, asymmetrically substituted, bulky ligand transition metal metallocene-type catalyst compound, at least one activator, and at least one carrier.
• the bridged, bulky ligand metallocene-type catalyst compound is mixed the bridged, asymmetrically substituted, bulky ligand metallocene-type catalyst compound to form a catalyst mixture; and then contacting the catalyst mixture with a carrier.
• the invention provides for a polymerization process using the supported mixed catalyst as described above.
• Figure 1 illustrates the Melt Index Ratio versus Melt Index data for the polymers produced as represented in Tables 3 and 4.
• the invention is directed toward a mixed metallocene-type catalyst system for polymerizing olefm(s), where the metallocene-type catalyst system includes at least two different bridged, metallocene-type catalyst compounds, a bridged, bulky ligand transition metal metallocene-type catalyst compound and a bridged, asymmetrically substituted bulky ligand, transition metal metallocene-type catalyst compound.
• the metallocene-type catalyst compounds are bridged in that there is a structural bridge imparting stereorigidity to the catalyst compounds. Also, the substitutions on one of the bridged, bulky ligand transition metal metallocene-type catalyst compounds is in an asymmetrical configuration on the bulky ligand.
• the polymer produced using the mixed catalyst of the invention has better processability than the polymers produced using a bridged, bulky ligand metallocene-type catalyst by itself and the polymer produced using the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst by itself. Furthermore, blending these two separately produced and different polymers does not result in a polymer blend having the processability characteristics of the polymer produced using the mixed catalyst of the invention. It has been surprisingly discovered that using a bridged bulky ligand metallocene-type catalyst compound and a bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound an improved polymer product is produced. In fact, the product produced using the mixed metallocene-type catalysts of the invention exhibit a melt index ratio greater than that of either of the separately produced polymers or blends of the separately produce polymers.
• the mixed catalyst of the invention produces a polymer product that is easier to process.
• a synergistic effect is observed in the polymer's high Melt Index
• MIR Melt Index Ratio
• bulky ligand transition metallocene-type catalyst compounds include half and full sandwhich compounds having one or more bulky ligands including cyclopentadienyl structures or other similar functioning structure such as pentadiene, cyclooctatetraendiyl and imides.
• the bulky ligands are capable of ⁇ -5 bonding to a transition metal atom, for example from Group 4, 5 and 6 of the Periodic Table of Elements.
• Non- limiting examples of catalyst components and catalyst systems are discussed in for example, U.S. Patent Nos.
• bridged, bulky ligand metallocene-type catalyst compounds of the invention are represented by the formula:
• M is a metal from the Periodic Table of the Elements and may be a Group 3 to 10 metal, preferably, a Group 4, 5 or 6 transition metal or a metal from the lanthanide or actinide series, more preferably M is a transition metal from Group 4, even more preferably zirconium, hafnium or titanium.
• L A and L B are bulky ligands that includes cyclopentadienyl derived ligands or substituted cyclopentadienyl derived or heteroatom substituted cyclopentadienyl derived ligands or hydrocarbyl substituted cyclopentadienyl derived ligands or moieties such as indenyl ligands, a benzindenyl ligands or a fluorenyl ligands, an octahydrofluorenyl ligands, a cyclooctatetraendiyl ligands, an azenyl ligands and the like, including hydrogenated versions thereof.
• L A and L B may be any other ligand structure capable of ⁇ -5 bonding to M, for example L A and L B may comprises one or more heteroatoms, for example, nitrogen, silicon, germanium, and phosphorous, in combination with carbon atoms to form a cyclic structure, for example a heterocyclopentadienyl ancillary ligand.
• each of L A and L B may also be other types of bulky ligands including but not limited to bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
• Each L A and L B may be the same or different type of bulky ligand that is ⁇ -bonded to M.
• Each L A and L B may be substituted with a combination of substituent groups R.
• substituent groups R include hydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl, alkynl or aryl radicals or combination thereof having from 1 to 30 carbon atoms or other substituents having up to 50 non-hydrogen atoms that can also be substituted.
• Non- limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, iso propyl etc.
• hydrocarbyl radicals include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methyl-bis (difTuoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamino, dimethylphosphino, diphenylamino, methylphenylphosphino, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide, ethyl
• Non-hydrogen substituents R include the atoms carbon, silicon, nitrogen, oxygen, tin, germanium and the like including olefins such as but not limited to olefmically unsaturated substituents including vinyl-terminated ligands, for example but-3-enyl or hexene-5. Also, two adjacent R groups are joined to form a ring structure having from 4 to 20 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, boron or a combination thereof. Other ligands may be bonded to the transition metal, such as a leaving group Q. Each Q may be an independently monoanionic labile ligand(s) having a sigma-bond to M.
• Each Q may be a neutral radical or a radical in a - 2 oxidation state.
• Q include weak bases such as amines, phosphines, ether, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like.
• Other examples of Q radicals include those substituents for R as described above and including cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene and pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
• bridged, bulky ligand metallocene-type catalyst compounds of the invention are those where L A and L B are bridged to each other by a bridging group A.
• bridging group A include bridging radicals of at least one Group 14 atom, such as but not limited to carbon, oxygen, nitrogen, silicon, germanium and tin, preferably carbon, silicon and germanium, most preferably silicon.
• bridging groups A include dimethylsilyl, diethylsilyl, methylethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di-n-butylsilyl, silylcyclobutyl, di-i-propylsilyl, di-cyclohexylsilyl, di-phenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di-t-butylphenylsilyl, di(p- tolyl)silyl, dimethylgermyl, diethylgermyl, methylene, dimethylmethylene, diphenylmethylene, ethylene, 1-2-dimethylethylene, 1,2-diphenylethylene, 1 , 1 ,2,2-tetramethylethylene, dimethylmethylenedimethylsilyl, methyl enediphenylgermyl, methyl
• M is a Group 4, 5 , 6 transition metal
• (C5H4_ d R d ) is an unsubstituted or substituted cyclopentadienyl derived bulky ligand bonded to M
• each R which can be the same or different, is hydrogen or a substituent group containing up to 50 non-hydrogen atoms or substituted or unsubstituted hydrocarbyl having from 1 to 30 carbon atoms or combinations thereof , or two or more carbon atoms are joined together to form a part of a substituted or unsubstituted ring or ring system having 4 to 30 carbon atoms
• A is one or more of, or a combination of carbon, germanium, silicon, tin, phosphorous or nitrogen atom containing radical bridging two (C5H4_ d R d ) rings; more particularly, non-limiting examples of A may be represented by R' 2 C, R' 2 Si, R' 2 Si R' 2 Si, R' 2 Si R' 2 C
• the bridged, bulky ligand metallocene-type compounds are those where the R substituents on the bulky ligands L A , L B , (C5H4_ d R d ) of formulas (I) and (II) are substituted with the same number of substituents on each of the bulky ligands.
• bridged, bulky ligand metallocene-type catalyst compounds of the invention include, dimethylsilyl-bis (cyclopentadienyl) zirconium dichloride, dimethylsilyl bis-(tetrahydroindenyl) zirconium dichloride, dimethylsilyl bis (indenyl) zirconium dichloride, dimethylsilyl bis (2-methyl-indenyl) zirconium dichloride, dimethylsilyl bis(l,2-di-methyl-cyclopentadienyl) zirconium dichloride, and any of the above catalyst compounds where the dimethylsilyl is an A as defined above, the methyl is an R as defined above, the bulky ligand (cyclopentadienyl, tetrahydroindenyl, indenyl) is as defined above for L A , L B , (C5H4_ d R ),
• the bulky ligand (C5H4_ R ) of formula (II) above is such that the integer d for each bulky ligand is the same integer from
• d is an integer from 0 to 3, more preferably from 0 to 2 and most preferably d is 2.
• a in formula (I) and (II) is a radical of one or more silicon atoms and the R substituents on each bulky ligand is hydrogen or the same number and kind of hydrocarbyl radical having from 1 to 30 carbon atoms, preferably 1 to 10, more preferably 1 to 5, and most preferably the R substituents are all hydrogen.
• bulky ligand metallocene-type catalyst compounds include bridged, symmetrically substituted bulky ligand metallocene-type compounds in terms of the type of substituent(s) R substituted on the bulky ligand. Bridged. Asymmetrically Substituted Bulky Ligand Metallocene-Type Catalyst Compounds
• the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compounds of the invention are represented by the above formula (I) where the L A and L B bulky ligands are asymmetrically substituted in terms of additional substituents or types of substituents, and/or unbalanced in terms of the number of additional substituents on the bulky ligands or the bulky ligands themselves are different.
• the bulky ligands are the same; however, the substituents R on each of L A and L B are different in number.
• R substituents may vary depending on the bulky ligand, however, preferably there are in the range of from 1 to 7 R substituent(s) between the two bulky ligands L A and L B .
• the definitions for L A and L B and R are as described above.
• the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compounds of the invention are represented by the above described formula (II) where the two bulky ligands (C5H4_ d R d ) as described above are different in terms of the number of R substituent groups on each of the bulky ligands (C5H4_ R d ).
• the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compounds of the invention may be represented by the above formula (II) where the value for d is different for each bulky ligand (C5H4_ d R ), more particularly and depending on the bulky ligand, d is an integer from 0, 1 , 2, 3 or 4 as defined above, where the integer d of one of the bulky ligands (C5H4_ d R ) is different from the other.
• the bulky ligands C5H4_ d R
• formula (II) is replaced with formula (III) represented by (C5H4_ d R d )A(C5H4_ e R e )MQg-2 , where A, R, Q, M and g are as defined above in formula (II); however, in formula (III) d and e are integers from 0 to 4, the sum of d and e equals 1 through 8, preferably the sum of d and e is 3 to 8, more preferably 3 to 5.
• d is equal to 4 and e is an integer from 0 to 3, preferably e is an integer from 0 to 2, and in the most preferred embodiment, e is l.
• a in formula (I) and (II) and (III) is a radical of one or more silicon atoms and the R substituents on each bulky ligand are the same hydrocarbyl radical having from 1 to 30 carbon atoms, preferably 1 to 10, more preferably 1 to 5, and even more preferably the R substituents are selected from one or more of methyl, ethyl, propyl and iso-propyl, and most preferably methyl, most preferred is where the R substituents are the same type of radical on each bulky ligand.
• Non-limiting examples of bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compounds of the invention include dimethylsilyl (1 ,2,3,4-tetramethyl cyclopentadienyl)(cyclopentadienyl)zirconium dichloride, dimethylsilyl (1 ,2,3,4-tetramethyl cyclopentadienyl)(l ,2,3-trimethyl- cyclopentadienyl)zirconium dichloride, dimethylsilyl (1,2,3,4-tetramethyl cyclopentadienyl)( 1 ,2-dimethyl-cyclopentadienyl)zirconium dichloride, dimethylsilyl (1 ,2,3,4-tetramethyl-cyclopentadienyl)(2- methylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl)(indenyl) zirconium dichlor
• mixed catalysts of the invention may include their structural or optical isomers and mixtures thereof.
• a single, bridged, asymmetrically substituted bulky ligand metallocene-type compound having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene-type catalyst compounds.
• the mixed catalyst of the invention is composed of at least one chiral, more preferably two chiral, bridged metallocene-type compounds of the invention where the bridged, bulky ligand metallocene-type compound of the invention is not substituted in the two position on the bulky ligand, more preferably is not a bridged, a 2-methyl- indenyl ligand.
• the mixed catalyst has from 1 to 99 mole percent of the bridged, bulky ligand metallocene-type catalyst compound to from 99 to 1 mole percent of the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound based on the total moles of the bridged, bulky ligand metallocene-type catalyst compound and the bridged, asymmetrically substituted, bulky ligand metallocene-type compound
• the mixed catalyst of the invention has from about 2 to about 98 mole percent of the bridged, bulky ligand metallocene-type catalyst compound to from about 98 to about 2 moles of the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound, more preferably from about 95 to about 5 mole percent of the bridged, bulky ligand metallocene-type catalyst compound to from about 5 to about 95 mole percent of the bridged, asymmetrically substituted bulky ligand metallocene
• the mole percent range of the mixed catalyst of the invention is from about 85 to about 15 mole percent of the bridged, bulky ligand metallocene-type catalyst compound to from about 15 to about 85 mole percent of the bridged, asymmetrically substituted bulky ligand metallocene- type catalyst compound. In the most preferred embodiment, the mole percent range of the mixed catalyst of the invention has from about 25 to about 75 mole percent of the bridged, bulky ligand metallocene-type catalyst compound to from about 75 to about 25 mole percent of the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound.
• bridged, bulky ligand metallocene-type catalyst compounds and the bridged, asymmetrically substituted, bulky ligand metallocene-type catalyst compounds of the invention are typically activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert, and polymerize olefins.
• activator is defined to be any compound or component or method which can activate any of the bridged, bulky ligand metallocene-type catalyst compounds and the bridged, asymmetrically substituted, bulky ligand metallocene-type catalyst compounds of the invention as described above.
• Non-limiting activators for example may include a Lewis acid or a non- coordinating ionic activator or ionizing activator or any other compound that can convert a neutral bulky ligand metallocene-type catalyst component to a bulky ligand metallocene cation.
• alumoxane or modified alumoxane as an activator, and/or to also use ionizing activators, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenyl boron metalloid precursor that would ionize the neutral metallocene compound.
• Ionizing compounds may contain an active proton, or some other cation associated with but not coordinated to or only loosely coordinated to the remaining ion of the ionizing compound.
• Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299 and 5,502,124 and U.S. Patent Application
• activators include those described in PCT publication WO 98/07515 such as tris (2, 2', 2"- nonafluorobiphenyl) fluoroaluminate, which publication is fully incorporated herein by reference.
• Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, PCT publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410 all of which are herein fully incorporated by reference.
• methods of activation such as using radiation and the like are also contemplated as activating methods for the purposes of rendering the neutral metallocene-type catalyst compound or precursor to a metallocene-type cation capable of polymerizing olefins.
• other catalysts can be combined with the mixed bridged, bulky ligand and asymmetrically substituted bulky ligand, metallocene-type catalyst compounds of the invention. For example, see U.S. Patent Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of which are herein fully incorporated herein reference.
• One such other catalyst useful in combination with the mixed bridged catalysts of the invention may be metallocene-type catalyst compounds that are known as bis-metallocene-type compounds as described in U.S. Patent No. 5,324,800, which is fully incorporated herein by reference.
• Other metallocene- type catalysts that may be combined with the mixed bridged catalysts of the invention include monocyclopentadienyl heteroatom containing transition metal metallocene-type compounds. These types of catalyst systems are described in, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/ 04257, WO 94/03506, WO96/00244 and WO 97/15602 and U.S. Patent
• catalysts that be combined with the mixed bridged catalysts of the invention may include those described in U.S. Patent Nos. 5,064,802,
• the mixed bridged catalysts of the invention may be used in combination with a non-metallocene or traditional Ziegler-Natta catalyst (excludes a cyclopentadienyl containing moiety) or catalyst system, or chromium based catalysts or catalyst systems, non-limiting examples are described in U.S. Patent Nos. 4,159,965, 4,325,837,
• the above described complexes can be combined with one or more of the catalyst compounds represented by formula (I) and (II), with one or more activators, and optionally with one or more of the support materials using one of the support methods described below.
• the mixed bridged, bulky ligand and asymmetrically substituted, bulky ligand metallocene-type catalyst systems of the invention may be made and used in a variety of different ways as described below.
• the mixed bridged catalyst of the invention is used in an unsupported form, preferably in a liquid form such as described in U.S.
• the catalyst in liquid form can be fed to a reactor as described in PCT publication WO 97/46599, which is fully incorporated herein by reference.
• the mixed bridged metallocene-type catalyst systems of the invention may be used in a supported form, for example deposited on, contacted with, or incorporated within, a support material.
• carrier or “support” are interchangeable and can be any support material, preferably a porous support material, for example, talc, inorganic oxides, inorganic chlorides, and magnesium chloride, and resinous support materials such as polystyrene or a functionalized organic support or crosslinked organic support such as polystyrene divinyl benzene polyolefins or polymeric compounds, or any other organic or inorganic support material and the like, or mixtures thereof.
• the preferred support materials are inorganic oxide materials, which include those of Groups 2, 3, 4, 5, 13 or 14 metal oxides.
• the mixed metallocene-type catalyst support materials include silica, alumina, silica-alumina, and mixtures thereof.
• inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina, and magnesia, titania, zirconia, montmorillonite and the like or combination thereof, for example, silica-chromium, silica-titania.
• the carrier of the mixed bridge metallocene-type catalysts of this invention preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m ⁇ /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 10 to about 500 ⁇ m. More preferably, the surface area is in the range of from about 50 to about 500 rn ⁇ /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 20 to about 200 ⁇ m.
• the surface area range is from about 100 to about 400 m ⁇ /g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 20 to about 100 ⁇ m.
• the average pore size of the carrier of the invention typically has pore size in the range of from 10 to lOOOA, preferably 50 to about 50 ⁇ A, and most preferably 75 to about 35 ⁇ A. Examples of supporting the mixed bridged metallocene-type catalyst systems of the invention are described in U.S. Patent Nos.
• the mixed bridged metallocene-type catalyst compounds of the invention may be deposited on the same or separate supports together with an activator, or the activator may be used in an unsupported form, or may be deposited on a support different from the supported mixed bridged metallocene-type catalyst compounds of the invention, or any combination thereof.
• the mixed bridged metallocene-type catalyst system of the invention contains a polymer bound ligand as described in U.S. Patent No. 5,473,202 which is herein fully incorporated by reference.
• the mixed bridged metallocene-type catalyst system of the invention is spray dried as described in U.S. Patent No. 5,648,310 which is fully incorporated herein by reference.
• the support used with the mixed bridged metallocene-type catalyst system of the invention is functionalized as described in European publication EP-A-0 802 203, or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880, both of which are herein fully incorporated by reference.
• olefm(s), preferably C2 to C30 olefm(s) or alpha-olefm(s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the mixed bridged metallocene-type catalyst system of the invention prior to the main polymerization.
• the prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures.
• the prepolymerization can take place with any alpha-olefm monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen.
• any molecular weight controlling agent such as hydrogen.
• the invention provides for a supported mixed bridged metallocene-type catalyst system that includes an antistatic agent or surface modifier, for example, those described in U.S. Patent No. 5,283,278 and PCT publication WO 96/11960 which are herein fully incorporated by reference.
• antistatic agents and surface modifiers include alcohol, thiol, silanol, diol, ester, ketone, aldehyde, acid, amine, and ether compounds.
• the antistatic agent can be added at any stage in the formation of the supported mixed bridged metallocene-type catalyst system of the invention, however, it is preferred that it is added after the supported mixed catalyst system of the invention is formed, in either a slurry or dried state.
• the mixed bridged, metallocene-type catalyst compound is slurried in a liquid to form a metallocene solution and a separate solution is formed containing an activator and a liquid.
• the liquid can be any compatible solvent or other liquid capable of forming a solution or the like with at least one of the bridged, metallocene-type catalyst compounds of the invention and/or at least one activator.
• the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.
• the mixed bridged metallocene-type catalyst compound and activator solutions are mixed together and added to a porous support or the porous support is added to the solutions such that the total volume of the mixed bridged, metallocene-type catalyst compound solution and the activator solution or the mixed bridged, metallocene-type catalyst compound and activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
• the mole ratio of the metal of the activator component to the metal of the mixed bridged, metallocene-type catalyst compounds are in the range of ratios between 0.3:1 to 1000:1, preferably 20:1 to 800:1, and most preferably 50:1 to 500:1.
• the activator is an aluminum- free ionizing activator such as those based on the anion tetrakis(pentafluorophenyl)boron
• the mole ratio of the metal of the activator component to the transition metal component is preferably in the range of ratios between 0.3:1 to 3:1.
• the mixed bridged metallocene-type catalyst compounds loadings in millimoles (mmoles) of metallocene-type catalyst compounds to weight of the supported mixed metallocene-type catalyst compounds in grams (g) is in the range of from about 0.001 to about 2.0 mmoles of metallocenes per g of support material, preferably from about
• 0.005 to about 1.0 more preferably from about 0.005 to 0.5 and most preferably from about 0.01 to 0.05.
• the bridged, bulky ligand metallocene- type catalyst compound and the bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound are codeposited on the same carrier.
• the mixed bridged metallocene-type catalyst compounds are combined with an activator prior to codepositing them onto a carrier. It is contemplated in the method of the invention that each of the bridged, metallocene-type catalyst compounds may be contacted with the same or different or a combination of activators to produce a supported mixed bridged metallocene-type catalyst system followed then by depositing the supported catalyst system onto the carrier.
• first supported catalyst system of a bridged, bulky ligand metallocene-type catalyst compound and to prepare a second catalyst system, preferably a supported catalyst system of a bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound such that the first and second supported catalyst systems are then combined to form a mixed supported catalysts system of the invention.
• the mixed bridged metallocene-type catalyst compounds and catalyst systems of the invention described above are suitable for use in any polymerization process.
• the polymerization process of the invention includes a solution, gas or slurry process (including a high pressure process) or a combination thereof, more preferably a gas or slurry phase process, and most preferably a gas phase process in a single reactor.
• this invention is directed toward the solution, slurry or gas phase polymerization or copolymerization reactions involving the polymerization of one or more of the olefin monomer(s) having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.
• the invention is particularly well suited to the copolymerization reactions involving the polymerization of one or more olefin monomers of ethylene, propylene, butene- 1 , pentene- 1 , 4-methyl-pentene- 1 , hexene- 1 , octene-1, decene-1, and cyclic olefins or a combination thereof
• Other monomers can include vinyl monomers, diolefins such as dienes, polyenes, norbornene, norbornadiene monomers.
• a copolymer of ethylene is produced, where the comonomer is at least one alpha-olefm having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms.
• ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer; the preferred comonomers are a combination of alpha-olefm monomers having 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, optionally with at least one diene monomer.
• the preferred terpolymers include the combinations such as ethylene/butene-1 /hexene- 1, ethylene/propylene/butene-1, propylene/ethylene/hexene-1, ethylene/propylene/ norbornene and the like.
• the process of the invention relates to the polymerization of ethylene and at least one comonomer having from 4 to
• the comonomers are butene- 1, 4-methyl-pentene- 1, hexene- 1 and octene- 1 , the most preferred being hexene- 1.
• a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
• a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
• the reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
• the reactor temperature in the gas phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 115°C, more preferably in the range of from about 70°C to 110°C, and most preferably in the range of from about 70°C to about 95°C.
• Other gas phase processes contemplated by the process of the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A- 0 794 200, EP-A- 0 802 202 and EP-B- 634 421 all of which are herein fully incorporated by reference.
• a slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even greater and temperatures in the range of 0°C to about 120°C.
• a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
• the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
• the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
• the medium employed should be liquid under the conditions of polymerization and relatively inert.
• a propane medium When used the process must be operated above the reaction diluent critical temperature and pressure.
• a hexane or an isobutane medium is employed.
• a preferred polymerization technique of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
• a particle form polymerization or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
• Such technique is well known in the art, and described in for instance U.S. Patent No. 3,248,179 whichis fully incorporated herein by reference.
• Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
• Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
• other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference. Examples of solution processes are described in U.S. Patent Nos.
• a preferred process of the invention is where the process, preferably a slurry or gas phase process is operated in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri- isobutylaluminum and tri-n-hexylaluminum and di ethyl aluminum chloride, dibutyl zinc and the like.
• any scavengers such as triethylaluminum, trimethylaluminum, tri- isobutylaluminum and tri-n-hexylaluminum and di ethyl aluminum chloride, dibutyl zinc and the like.
• the polymers typically have a density in the range of from 0.86g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.900 g/cc, preferably greater than 0.910 g/cc, and most preferably greater than 0.915 g/cc.
• the polymers produced by the mixed catalyst system of the invention have a density in the range of from 0.910 g/cc to about 0.930 g/cc, most preferably in the range of from 0.915 g/cc to about 0.930 g/cc.
• the polymers of the invention typically may have a relatively narrow molecular weight distribution, a weight average molecular weight to number average molecular weight (M ⁇ /MJ of greater than 1.5 to about 10, particularly greater than 2 to about 8, more preferably greater than about 4 to less than 8. Also, the polymers of the invention typically have a narrow composition distribution as measured by Composition Distribution Breadth Index (CDBI). Further details of determining the CDBI of a copolymer are known to those skilled in the art. See, for example, PCT Patent Application WO 93/03093, published February 18, 1993 which is fully incorporated herein by reference.
• CDBI Composition Distribution Breadth Index
• the polymers of the invention in one embodiment have CDBI's generally in the range of greater than 50% to 99%, preferably in the range of 55%) to 85%), and more preferably 60% to 80%, even more preferably greater than 60%), still even more preferably greater than 65%>.
• the polymers of the present invention in one embodiment have a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E in the range from 0.01 dg/min to 1000 dg/min, more preferably from about 0.05 dg/min to about 200 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.3 dg/min to about 20 dg/min.
• MI melt index
• I 2 melt index
• the polymers of the invention in one embodiment have a melt index ratio (I 21 /I 2 ) as measured above of from preferably greater than 50, more preferably greater than 55, and most preferably greater than 60.
• the polymers of the invention in another embodiment satisfy the following formula MIR > 0.95[58.352-63.498(log(MI))], where MI is the melt index as measured above.
• the polymers of the invention have a density in the range of from 0.85 g/cc to about 0.950 g/cc and satisfy the following formula MIR > [58.352-63.498(log(MI))], where MI is the melt index as measured above.
• the MIR in either equation above is not a negative number, and it is preferred that the MI in either equation is preferably less than about 8 dg/min, more preferably in the range of from 0.01 dg/min to about 5 dg/min and most preferably in the range of from 0.1 dg/min to about 3 dg/min.
• Polymers produced by the process of the invention are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
• Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and non-food contact applications.
• Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
• Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
• MWD or polydispersity
• Mw weight average molecular weight
• Mn number average molecular weight
• Mw/Mn can be measured by gel permeation chromatography techniques well known in the art.
• MAO methylalumoxane
• Me 2 Si( ⁇ 5 -CpMe 4 )( ⁇ 5 -3MeC 5 H 3 )ZrCl 2 , in 834 ml toluene was transferred into the reactor vessel via a cannula.
• the mixture was removed from the reactor to a large glass flask and 895.2 g of silica gel (MS948, 1.65 cc/g P. V., available from W.R. Grace, Davison Chemical Division, Baltimore, Maryland) was added to the reactor vessel.
• the activated metallocene solution was then added back to the reactor vessel and stirred for 20 min.
• N,N-bis(2-hydroxylethyl) octadecylamine ((C ⁇ 8 H3 7 N(CH2CH 2 OH)2) is available as Kemamine AS-990 from ICI Specialties, Wilmington, Delaware) in about 70 mL toluene was added and stirring continued another 20 min. Drying was then begun by gradually evacuating the system to >27 in Hg vacuum while feeding a small stream of N2 into the bottom of the reactor with heating and stirring. After 7.5 hr 1293 g of free flowing, dry material was unloaded from the reactor vessel under N 2 pressure.
• the catalyst systems of Comparative Examples 1 and Comparative Examples 2 were then tested in a continuous gas phase fluidized bed reactor which comprised a nominal 18 inch, schedule 60 reactor having an internal diameter of 16.5 inches.
• the fluidized bed is made up of polymer granules.
• the gaseous feed streams of ethylene and hydrogen together with liquid comonomer were mixed together in a mixing tee arrangement and introduced below the reactor bed into the recycle gas line. Hexene- 1 was used as the comonomer.
• the individual flow rates of ethylene, hydrogen and comonomer were controlled to maintain fixed composition targets.
• the ethylene concentration was controlled to maintain a constant ethylene partial pressure.
• the hydrogen was controlled to maintain a constant hydrogen to ethylene mole ratio.
• concentration of all the gases were measured by an on-line gas chromatograph to ensure relatively constant composition in the recycle gas stream.
• the catalyst system was injected directly into the fluidized bed using purified nitrogen as a carrier. Its rate was adjusted to maintain a constant production rate.
• the reacting bed of growing polymer particles is maintained in a fluidized state by the continuous flow of the make up feed and recycle gas through the reaction zone. A superficial gas velocity of 1 -3 ft/sec was used to achieve this.
• the reactor was operated at a total pressure of 300 psig. To maintain a constant reactor temperature, the temperature of the recycle gas is continuously adjusted up or down to accommodate any changes in the rate of heat generation due to the polymerization.
• the fluidized bed was maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of formation of particulate product.
• the product is removed semi- continuously via a series of valves into a fixed volume chamber, which is simultaneously vented back to the reactor. This allows for highly efficient removal of the product, while at the same time recycling a large portion of the unreacted gases back to the reactor.
• This product is purged to remove entrained hydrocarbons and treated with a small steam of humidified nitrogen to deactivate any trace quantities of residual catalyst.
• Comparative Example 3 a physical blend ratio of 75 percent of the polymer produced using the polymer produced using the catalyst system of Comparative Example 1 (Polymerization Process CEx 1) and 25 percent of the polymer produced using the catalyst system of Comparative Example 2 (Polymerization Process CEx 2).
• the resulting polymer blend had a density of 0.919 g/cc, a melt index of 0.88 dg/min and a MIR of 51. See Table 3, CEx 3 for more results. Comparative Example 4
• Comparative Example 3 a physical blend ratio of 50 percent of the polymer produced using the polymer produced using the catalyst system of Comparative Example 1 (Polymerization Process CEx 1) and 50 percent of the polymer produced using the catalyst system of Comparative Example 2 (Polymerization Process CEx 2).
• the resulting polymer blend had a density of 0.919 g/cc, a melt index of 0.87 dg/min and a MIR of 49. See Table 3, CEx 4 for more results. Comparative Example 5
• Comparative Example 1 Polymerization Process CEx 1
• 75 percent of the polymer produced using the catalyst system of Comparative Example 2 Polymerization Process CEx 2.
• the resulting polymer blend had a density of 0.918 g/cc, a melt index of 0.87 dg/min and a MIR of 47. See Table 3, CEx 5 for more results .
• Silica gel (36.3 g) is poured into the reaction mixture and mixed with a spatula. The wet solid is transferred to a glass bulb and dried in vacuo at room temperature for 15 h. It is transferred to a metal bomb for screening in lab gas phase reactor.
• Me 2 Si(C 9 H 10 ) 2 ZrCl 2 (0.37 g, 0.81 mmol) was added methylalumoxane (MAO) (24.2 g, 30% in toluene) and toluene (24.2 g) and the mixture was stirred until dissolution (10 min).
• MAO methylalumoxane
• Silica gel (18.2 g) is poured into the reaction mixture and mixed with a spatula. The wet solid is transferred to a glass bulb and dried in vacuo at room temperature for 15 h to form a supported Me 2 Si(C 9 H 10 ) 2 ZrCl 2 .
• Example 9B To a solid mixture of Me 2 Si( ⁇ 5 -CpMe 4 )( ⁇ 5 -3MeC 5 H 3 )ZrCl 2 (1.62 g,
• methylalumoxane (MAO) (108.1 g, 30% in toluene) and toluene (108.1 g) and the mixture was stirred until dissolution (10 min).
• Example 9A 13.8 g of the supported catalyst of Example 9A was then blended together with 37.2 g of the supported catalyst of Example 9B before loading into a metal bomb. The mixed supported catalysts were then transferred to a metal bomb for testing in a lab gas phase reactor. Polymerization conditions are set forth in Table 2 and polymer properties are set forth in Table 3. Lab Gas Phase Polymerizations for Examples 6 through 9
• All the catalysts prepared in Examples 6 through 9 were screened in a fluidized bed reactor equipped with devices for temperature control, catalyst feeding or injection equipment, GC analyzer for monitoring and controlling monomer and gas feeds and equipment for polymer sampling and collecting.
• the reactor consists of a 6" diameter bed section increasing to 10" at the reactor top. Gas comes in through a perforated distributor plate allowing fluidization of the bed contents and polymer sample is discharged at the reactor top.
• the mixed catalyst system of the invention produces polymer products having Melt Index Ratio values higher than each polymer produced separately by each of the different bridged metallocene-type catalysts of the invention (Comparative Examples 1 and 2), than various physical blends of the polymers produced from each bridged metallocene-type catalyst separately (Comparative Examples 3 through 5).
• Examples 6 and 7 clearly illustrate the higher MIR values using the mixed bridged, bulky ligand metallocene-type catalysts of the invention.
• Examples 8 and 9 have significantly higher Mi's than the comparative examples, their advantage in MIR is best illustrated in Figure 1 where the MI dependence of MIR is shown. Comparative Examples 10 and 11
• Comparative Example 10 The product of Comparative Example 10 was produced using the same bridged, asymmetrically substituted bulky ligand metallocene-type catalyst compound, Me 2 Si( ⁇ 5 -CpMe 4 )( ⁇ :, -3MeC 5 H 3 )ZrCl 2 , as described and prepared in Comparative Example 1.
• the supported catalyst system of Comparative Example 10 was tested in a lab gas phase polymerization process similar to that described above. The polymer results are set forth in Table 4 below.
• the product of Comparative Example 11 was produced using the same bridged, bulky ligand metallocene-type catalyst compound, Me2Si(H4lnd) 2 ZrCi2), as described and prepared in Comparative Example 2.
• the supported catalyst system of Comparative Example 11 was tested in a lab gas phase polymerization process similar to that described above.
• the polymer results are set forth in Table 4 below. Examples 12 through 14
• Example 12 The product of Example 12 was produced using the same mixed bridged metallocene-type catalysts compounds in the same proportions as described and similarly prepared as in Example 6 above.
• the supported catalyst system of Example 12 was tested in a lab gas phase polymerization process similar to that described above. The polymer results are set forth in Table 4 below.
• Example 13 The product of Example 13 was produced using the same mixed bridged metallocene-type catalysts compounds in the same proportions as described and similarly prepared as in Example 7 above.
• the supported catalyst system of Example 13 was tested in a lab gas phase polymerization process similar to that described above.
• the polymer results are set forth in Table 4 below.
• the product of Example 14 was produced using the same mixed bridged metallocene-type catalysts compounds in the same proportions as described and similarly prepared as in Example 7 above.
• the supported catalyst system of Example 14 was tested in a lab gas phase polymerization process similar to that described above.
• the polymer results are set forth in Table 4 below.
• FIG. 1 is a graph of the MIR versus Melt Index data from Tables 3 and 4. Note that the resulting polymers produced by the mixed bridged, metallocene-type catalyst systems of the inventions (including Example 9) have a higher MIR at a given MI.
• the mixed bridged metallocene-type catalyst systems of the invention may be mixed with an unbridged bulky ligand metallocene-type catalyst compound that may be optionally asymmetrically substituted. It is also contemplated that this mixed bridged metallocene-type catalyst compounds of the invention can be used separately or together in a series reactor process. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

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