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  • 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
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  • 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
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  • 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
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  • 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
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  • 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
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  • C08L2314/06—Metallocene or single site catalysts

Definitions

• the present invention relates to a catalyst composition including a Group 15 containing metal compound, and to a mixed catalyst composition including at least two metal compounds.
• at least one of the metal compounds of the mixed composition is the Group 15 containing metal compound.
• the other metal compound is a bulky ligand metallocene catalyst compound.
• the present invention also relates to catalyst systems utilizing the catalyst compositions, and to their use in olefin(s) polymerization.
• the present invention further relates to a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.
• Clark et al. "Titanium (IV) complexes incorporating the aminodiamide ligand [(SiMe 3 )N ⁇ CH 2 CH 2 N (SiMe 3 ) ⁇ 2 ] 2"( L); the X-ray crystal structure of [TiMe 2 (L)] and [TiCl ⁇ CH(SiMe 3 ) 2 ⁇ (L)]", Journal of Organometallic Chemistry, Vol 50, pp. 333-340, 1995; (8) Scollard et al., "Living Polymerization of alpha-olefins by Chelating Diamide Complexes of Titanium", J. Am. Chem. Soc, Vol 118, No. 41, pp.
• U.S. Patent No. 5,576,460 describes a preparation of arylamine ligands and U.S. Patent No. 5,889,128 discloses a process for the living polymerization of olefins using initiators having a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms.
• EP 893 454 Al also describes preferably titanium transition metal amide compounds.
• U.S. Patent No. 5,318,935 discusses amido transition metal compounds and catalyst systems especially for the producing isotactic polypropylene. Polymerization catalysts containing bidentate and tridentate ligands are further discussed in U.S. Patent No. 5,506,184.
• PCT patent application WO 99/03899 discloses using a typical bulky ligand metallocene catalyst and a conventional-type Ziegler-Natta catalyst in the same reactor to produce a bimodal polyolefin.
• Using two different types of catalysts result in a polymer whose characteristics cannot be predicted from those of the polymers that each catalyst would produce if utilized separately. This unpredictability occurs, for example, from competition or other influence between the catalyst or catalyst systems used.
• Polyethylenes with a higher density and a higher molecular weight are valued in film applications requiring high stiffness, good toughness and high throughput. Such polymers are also valued in pipe applications requiring stiffness, toughness and long-term durability, and particularly resistance to environmental stress cracking.
• the present invention provides for catalyst compounds, catalyst systems, and mixed catalyst systems, and for their use in polymerization processes, polymers produced therefrom, and products made from the polymer.
• the invention is directed to a catalyst compound including a Group 15 containing metal compound, and to a mixed catalyst composition including at least two metal compounds, where at least one metal compound of the mixed composition is the Group 15 containing metal compound, and where the other metal compound is a bulky ligand metallocene compound, a conventional transition metal catalyst, or combinations thereof, to catalyst systems including these catalysts, to their use in olefin(s) polymerization and to polymers made therefrom.
• the invention is directed to a Group 15 containing bidentate or tridentate ligated Group 3 to 14 metal compound, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal catalyst compound, and to a mixed catalyst composition including at least two metal compounds, where at least one metal compound is the Group 15 containing catalyst compound described above, and where the other metal compound is a bulky ligand metallocene compound, a conventional transition metal catalyst, or combinations thereof, to catalyst systems including these catalysts, to their use in olefin(s) polymerization and to polymers made therefrom.
• the other metal compound is a bulky ligand metallocene compound.
• the invention is directed to a Group 3 to 14 metal atom bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group catalyst compound, and to a mixed catalyst composition including at least two metal compounds, where one metal compound is the Group 15 containing catalyst compound described above, and where the second metal compound, is different from the first metal compound, and is a bulky ligand metallocene catalyst, a conventional-type transition metal catalyst, or combinations thereof, to catalyst systems including these catalysts, to their use in olefin(s) polymerization and to polymers made therefrom..
• the invention is directed to a method of supporting the catalysts compositions described herein, to the supported catalyst systems themselves, and to their use in olefin(s) polymerization.
• the invention is directed to the use of a Lewis acid aluminum containing activator with the catalyst compositions and systems described herein.
• the invention is directed to a method of feeding the catalyst compositions and systems described herein into a polymerization reactor in a liquid carrier.
• the invention is directed to a process for polymerizing olefin(s), particularly in a gas phase or slurry phase process, utilizing any one of the catalyst systems or supported catalyst systems described herein.
• the invention is directed to processes for polymerizing olefin(s) utilizing the mixed catalyst compositions described above, especially in a single polymerization reactor. More preferably, the process utilizes a continuous gas phase single reactor process producing a multimodal polymer.
• the invention is directed to the polymers prepared utilizing the above mixed catalyst composition, and preferably to a new bimodal MWD HDPE.
• Figure 1 is a graphic representation of Illustration 1 below
• Figure 2 is a graphic representation of Illustration 2 below
• Figure 3 is a graphic representation of Illustration 3 below
• Figure 4 is a graphic representation of Illustration 4 below
• Figure 5 is a graphic representation of Illustration 5 below
• Figure 6 is a graphic representation of Illustration 6 below
• Figure 7 is a graphic representation of Illustration 7 below
• Figure 8 is a graphic representation of Illustration 8 below
• Figure 9 is a graphic representation of Illustration 9 below.
• the present invention relates to the use of a Group 15 containing metal catalyst compound in olefin(s) polymerization.
• a Group 15 containing metal catalyst compound in combination with another catalyst, preferably a bulky ligand metallocene compound, produces a new bimodal MWD HDPE product.
• the mixed catalyst composition of the present invention may be utilized in a single reactor system.
• the Group 15 containing compound generally includes a Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal atom, bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group.
• At least one of the Group 15 atoms is also bound to a Group 15 or 16 atom through another group which may be a Ci to C 20 hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also be bound to nothing or a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two Group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.
• Group 15 containing metal compound of the present invention may be represented by the formulae:
• M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, preferably a
• each X is independently a leaving group, preferably, an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl.
• y is 0 or 1 (when y is 0 group L' is absent), n is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4, m is the formal charge of the YZL or the YZL' ligand, preferably 0, -1, -2 or -3, and more preferably -2,
• L is a Group 15 or 16 element, preferably nitrogen
• L' is a Group 15 or 16 element or Group 14 containing group, preferably carbon, silicon or germanium,
• Y is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen
• Z is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen
• R 1 and R 2 are independently a Ci to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, preferably a
• R 3 is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably R 3 is absent, hydrogen or an alkyl group, and most preferably hydrogen
• R and R 5 are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system, preferably having up to 20 carbon atoms, more preferably between 3 and 10 carbon atoms, and even more preferably a C ⁇ to C 20 hydrocarbon group, a Ci to C
• R and R are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably absent, and R is absent, or is hydrogen, a Group 14 atom containing group, a halogen, a heteroatom containing group.
• Formal charge of the YZL or YZL' ligand it is meant the charge of the entire ligand absent the metal and the leaving groups X.
• R 1 and R 2 may also be interconnected” it is meant that R 1 and R 2 may be directly bound to each other or may be bound to each other through other groups.
• R 4 and R 5 may also be interconnected” it is meant that R 4 and R 5 may be directly bound to each other or may be bound to each other through other groups.
• An alkyl group may be a linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof.
• An aralkyl group is defined to be a substituted aryl group.
• R 4 and R are independently a group represented by the following formula:
• R 8 to R 12 are each independently hydrogen, a Ci to C 40 alkyl group, a halide, a heteroatom, a heteroatom containing group containing up to 40 carbon atoms, preferably a Ci to C 20 linear or branched alkyl group, preferably a methyl, ethyl, propyl or butyl group, any two R groups may form a cyclic group and/or a heterocyclic group.
• the cyclic groups may be aromatic.
• R 9 , R 10 and R 12 are independently a methyl, ethyl, propyl or butyl group (including all isomers), in a prefe ⁇ ed embodiment R 9 , R 10 and R 12 are methyl groups, and R 8 and R 1 ' are hydrogen.
• R 4 and R 5 are both a group represented by the following formula:
• M is a Group 4 metal, preferably zirconium, titanium or hafnium, and even more preferably zirconium; each of L, Y, and Z is nitrogen; each of R and R is - CH 2 -CH 2 -; R 3 is hydrogen; and R 6 and R 7 are absent.
• At least one X is a substituted hydrocarbon group, preferably a substituted alkyl group having more than 6 carbon atoms, most preferably an aryl substituted alkyl group.
• the most preferably aryl substituted alkyl group is benzyl.
• the Group 15 containing metal compound is represented by the formula:
• Ph phenyl
• the Group 15 containing metal compounds of the invention are prepared by methods known in the art, such as those disclosed in EP 0 893 454 Al, U.S. Patent No. 5,889,128 and the references cited in U.S. Patent No. 5,889,128 which are all herein incorporated by reference.
• U.S. Application Serial Number 09/312,878, filed May 17, 1999 discloses a gas or slurry phase polymerization process using a supported bisamide catalyst, which is also incorporated herein by reference.
• a prefe ⁇ ed direct synthesis of these compounds comprises reacting the neutral ligand, (see for example YZL or YZL' of formula I or II) with M ⁇ X n (M is a Group 3 to 14 metal, n is the oxidation state of M, each X is an anionic group, such as halide, in a non-coordinating or weakly coordinating solvent, such as ether, toluene, xylene, benzene, methylene chloride, and/or hexane or other solvent having a boiling point above 60 °C, at about 20 to about 150 °C (preferably 20 to 100 °C), preferably for 24 hours or more, then treating the mixture with an excess (such as four or more equivalents) of an alkylating agent, such as methyl magnesium bromide in ether.
• the magnesium salts are removed by filtration, and the metal complex isolated by standard techniques.
• the Group 15 containing metal compound is prepared by a method comprising reacting a neutral ligand, (see for exampleYZL or YZL' of formula 1 or 2) with a compound represented by the formula M n X n (where M is a Group 3 to 14 metal, n is the oxidation state of M, each X is an anionic leaving group) in a non-coordinating or weakly coordinating solvent, at about 20 °C or above, preferably at about 20 to about 100 °C, then treating the mixture with an excess of an alkylating agent, then recovering the metal complex.
• a neutral ligand see for exampleYZL or YZL' of formula 1 or 2
• M is a Group 3 to 14 metal
• n is the oxidation state of M
• each X is an anionic leaving group
• the solvent has a boiling point above 60 °C, such as toluene, xylene, benzene, and/or hexane.
• the solvent comprises ether and/or methylene chloride, either being preferable.
• the Group 15 containing metal compound described above may be combined with a second metal compound to form a mixed catalyst composition.
• the second metal compound is preferably a bulky ligand metallocene compound.
• bulky ligand metallocene compounds include half and full sandwich compounds having one or more bulky ligands bonded to at least one metal atom.
• Typical bulky ligand metallocene compounds are generally described as containing one or more bulky ligand(s) and one or more leaving group(s) bonded to at least one metal atom.
• at least one bulky ligands is ⁇ -bonded to the metal atom, most preferably ⁇ 5 -bonded to the metal atom.
• the bulky ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof.
• These bulky ligands preferably the ring(s) or ring system(s) are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements, preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof.
• the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand.
• the metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements.
• the metal is a transition metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4.
• the bulky ligand metallocene catalyst compounds are represented by the formula:
• M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is a Group 4 transition metal, even more preferably M is zirconium, hafnium or titanium.
• the bulky ligands, L A and L B are open, acyclic or fused ring(s) or ring system(s) and are any ancillary ligand system, including unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and or heteroatom containing cyclopentadienyl-type ligands.
• Non- limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125), py ⁇ olyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands.
• L A and L B may be any other ligand structure capable of ⁇ -bonding to M, preferably ⁇ -bonding to M and most preferably ⁇ -bonding .
• the atomic molecular weight (MW) of L A or L B exceeds 60 a.m.u., preferably greater than 65 a.m.u..
• L A and L B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a hetero-cyclopentadienyl ancillary ligand.
• L A and L B bulky ligands include but are 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. In one embodiment of formula (III) only one of either L A or L B is present.
• each L A and L B may be unsubstituted or substituted with a combination of substituent groups R.
• Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof.
• substituent groups R have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like.
• 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, isopropyl, and the like.
• 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(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulf
• Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to olefmically unsaturated substituents including vinyl- terminated ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof. Also, a substituent group R group such as 1-butanyl may form a carbon sigma bond to the metal M.
• ligands may be bonded to the metal M, such as at least one leaving group Q.
• Q is a monoanionic labile ligand having a sigma-bond to M.
• n is 0, 1 or 2 such that formula (III) above represents a neutral bulky ligand metallocene catalyst compound.
• Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof.
• weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof.
• two or more Q's form a part of a fused ring or ring system.
• Q ligands include those substituents for R as described above and including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
• the bulky ligand metallocene catalyst compounds of the invention include those of formula (III) where L A and L B are bridged to each other by at least one bridging group, A, such that the formula is represented by
• bridging group A include bridging groups containing at least one Group 13 to 16 atom, often refe ⁇ ed to as a divalent moiety such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or a combination thereof.
• bridging group A contains a carbon, silicon or germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom.
• the bridging group A may also contain substituent groups R as defined above including halogens and iron.
• Non-limiting examples of bridging group A may be represented by R' 2 C, R' 2 Si, R' 2 Si R' 2 Si, R' 2 Ge, R'P, where R' is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl- substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen or two or more R' may be joined to form a ring or ring system.
• the bridged, bulky ligand metallocene catalyst compounds of formula (IV) have two or more bridging groups A (EP 664 301 Bl).
• the bulky ligand metallocene catalyst compounds are those where the R substituents on the bulky ligands L A and L B of formulas (III) and (IV) are substituted with the same or different number of substituents on each of the bulky ligands.
• the bulky ligands L A and L B of formulas (III) and (IV) are different from each other.
• bulky ligand metallocene catalysts compounds useful in the invention include bridged heteroatom, mono-bulky ligand metallocene compounds.
• These types of catalysts and catalyst systems are described in, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/ 04257, WO 94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all of which are herein fully incorporated by reference.
• the bulky ligand metallocene catalyst compound is represented by the formula:
• M is a Group 3 to 16 metal atom or a metal selected from the Group of actinides and lanthanides of the Periodic Table of Elements, preferably M is a Group 4 to 12 transition metal, and more preferably M is a Group 4, 5 or 6 transition metal, and most preferably M is a Group 4 transition metal in any oxidation state, especially titanium; L is a substituted or unsubstituted bulky ligand bonded to M; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillary ligand; and A is a bridging group; Q is a univalent anionic ligand; and n is the integer 0,1 or 2.
• L c , A and J form a fused ring system.
• L c of formula (V) is as defined above for L A , A, M and Q of formula (V) are as defined above in formula (III).
• J is a heteroatom containing ligand in which J is an element with a coordination number of three from Group 15 or an element with a coordination number of two from Group 16 of the Periodic Table of Elements.
• J contains a nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being most prefe ⁇ ed.
• the bulky ligand metallocene- type catalyst compounds are heterocyclic ligand complexes where the bulky ligands, the ring(s) or ring system(s), include one or more heteroatoms or a combination thereof.
• heteroatoms include a Group 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examples of these bulky ligand metallocene catalyst compounds are described in WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-Al-0 874 005 and U.S. Patent No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporated by reference.
• the bulky ligand metallocene catalyst compounds are those complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. Application Serial No. 09/103,620 filed June 23, 1998, which is herein incorporated by reference.
• the bulky ligand metallocene catalyst compounds are those described in
• the bulky ligand type metallocene catalyst compound is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bonded ligand, and one or more heteroallyl moieties, such as those described in U.S. Patent Nos. 5,527,752 and 5,747,406 and EP-Bl-0 735 057, all of which are herein fully incorporated by reference.
• any one of the bulky ligand metallocene catalyst compounds of the invention have at least one fluoride or fluorine containing leaving group as described in U.S. Application Serial No. 09/191,916 filed November 13, 1998.
• the other metal compound or second metal compound is the bulky ligand metallocene catalyst compound is represented by the formula: L D MQ 2 (YZ)X n (VI)
• M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal;
• L D is a bulky ligand that is bonded to M; each Q is independently bonded to M and Q 2 (YZ) forms a ligand, preferably a unicharged polydentate ligand;
• a or Q is a univalent anionic ligand also bonded to M;
• X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is i; n is 1 or 2.
• L and M are as defined above for formula (III).
• Q is as defined above for formula (III), preferably Q is selected from the group consisting of -O-, -NR-, -CR2- and -S-; Y is either C or S; Z is selected from the group consisting of -OR, - N 2, -CR3, -SR, -SiR3, -PR2, -H, and substituted or unsubstituted aryl groups, with the proviso that when Q is -NR- then Z is selected from one of the group consisting of -OR, -NR2, -SR, -SiR3, -PR2 and -H; R is selected from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is an integer from 1 to 4, preferably 1 or 2;
• the bulky ligand metallocene compound is represented by the formula:
• the first and second metal compounds, described above may be combined at molar ratios of 1:1000 to 1000:1, preferably 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably 30:70 to 70:30, more preferably 40:60 to 60:40.
• the particular ratio chosen will depend on the end product desired and or the method of activation
• the metal compounds described herein are typically activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert and polymerize olefin(s).
• activator is defined to be any compound or component or method which can activate any of the Group 15 containing metal compounds and/or the bulky ligand metallocene 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 including Lewis bases, aluminum alkyls, conventional-type cocatalysts and combinations thereof that can convert a neutral bulky ligand metallocene catalyst compound or Group 15 containing metal compound to a catalytically active Group 15 containing metal compound or 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 tefrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983) or combination thereof, that would ionize the neutral bulky ligand metallocene catalyst and or the Group 15 containing metal compound.
• activators neutral or ionic, such as tri (n-butyl) ammonium tefrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO
• an activation method using ionizing ionic compounds not containing an active proton but capable of producing a Group 15 containing metal compound cation or bulky ligand metallocene catalyst cation and their non-coordinating anion are also contemplated, and are described in EP-A- 0 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
• Organoaluminum compounds useful as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.
• 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-Bl-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos.
• 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, EP-Bl 0 573 120, 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.
• WO 98/09996 incorporated herein by reference describes activating bulky ligand metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates.
• WO 98/30602 and WO 98/30603 incorporated by reference describe the use of lithium (2,2'-bisphenyl- ditrimethylsilicate) «4THF as an activator for a bulky ligand metallocene catalyst compound.
• WO 99/18135 incorporated herein by reference describes the use of organo-boron-aluminum activators.
• EP-Bl-0 781 299 describes using a silylium salt in combination with a non- coordinating compatible anion.
• methods of activation such as using radiation (see EP- Bl-0 615 981 herein incorporated by reference), electro-chemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral bulky ligand metallocene catalyst compound or precursor to a bulky ligand metallocene cation capable of polymerizing olefins.
• Other activators or methods for activating a bulky ligand metallocene catalyst compound are described in for example, U.S. Patent Nos.
• the activator is a Lewis acid compound, more preferably an aluminum based Lewis acid compound, and most preferably a neutral, aluminum based Lewis acid compound having at least one, preferably two, halogenated aryl ligands and one or two additional monoanionic ligands not including halogenated aryl ligands.
• the Lewis acid compounds of this embodiment include those olefin catalyst activator Lewis acids based on aluminum and having at least one bulky, electron-withdrawing ancillary ligand such as the halogenated aryl ligands of tris(perfluorophenyl)borane or tris(perfluoronaphthyl)borane.
• These bulky ancillary ligands are those sufficient to allow the Lewis acids to function as electronically stabilizing, compatible non-coordinating anions. Stable ionic complexes are achieved when the anions will not be a suitable ligand donor to the strongly Lewis acidic cationic Group 15 containing transition metal cations used in insertion polymerization, i.e., inhibit ligand transfer that would neutralize the cations and render them inactive for polymerization.
• at least one (ArHal) of formula (VII) is a halogenated C 9 aromatic or higher, preferably a fluorinated naphthyl.
• Suitable non-limiting R ligands include: substituted or unsubstituted Ci to C 0 hydrocarbyl aliphatic or aromatic groups, substituted meaning that at least one hydrogen on a carbon atom is replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid, dialkylamido, alkoxy, siloxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, alkylphosphido or other anionic substituent; fluoride; bulky alkoxides, where bulky refers to C 4 and higher number hydrocarbyl groups, e.g., up to about C 20 , such as tert-butoxide and 2,6-dimethyl-phenoxide, and 2,6-di(tert-butyl)phenoxide; -SR; -NR 2 , and -PR 2 , where each R
• ArHal examples include the phenyl, naphthyl and anthracenyl radicals of U.S. Patent No. 5,198,401 and the biphenyl radicals of WO 97/29845 when halogenated.
• halogenated or halogenation means for the purposes of this application that at least one third of hydrogen atoms on carbon atoms of the aryl-substituted aromatic ligands are replaced by halogen atoms, and more prefe ⁇ ed that the aromatic ligands be perhalogenated. Fluorine is the most prefe ⁇ ed halogen.
• the mole ratio of the metal of the activator component to the metal of a supported Group 15 containing catalyst compound are in the range of 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 ionizing activator such as those based on the anion tetrakis(penta- fluorophenyl)boron
• the mole ratio of the metal of the activator component to the metal component of the Group 15 containing hafnium catalyst compound is preferably in the range of between 0.3:1 to 3:1.
• Group 15 containing metal compounds and/or the bulky ligand metallocene catalyst compounds can be combined with one or more of the catalyst compounds represented by formulas (III) through (VI) with one or more activators or activation methods described above.
• modified alumoxanes are combined with the first and second metal compounds of the invention to form a catalyst system.
• MMAO3 A modified methyl alumoxane in heptane, commercially available from Akzo Chemicals, Inc., Holland, under the trade name Modified Methylalumoxane type 3A , see for example those aluminoxanes disclosed in U.S. Patent No. 5,041,584, which is herein incorporated by reference
• the prefe ⁇ ed weight percents are 10 to 95 weight % compound of Formula 1 and 5 to 90 weight % compound of Formula 2, preferably 50 to 90 weight % compound of Formula 1 and 10 to 50 weight % compound of Formula 2, more preferably 60 to 80 weight % compound of formula 1 to 40 to 20 weight % compound of formula 2.
• the compound of Formula 2 is activated with methylalumoxane, then combined with the compound of Formula 2, then injected in the reactor.
• the prefe ⁇ ed weight percents are 10 to 95 weight % Compound I and 5 to 90 weight % indenyl zirconium tris-pivalate, preferably 50 to 90 weight % Compound I and 10 to 50 weight % indenyl zirconium tris-pivalate, more preferably 60-80 weight % Compound I to 40 to 20 weight % indenyl zirconium tris-pivalate.
• the indenyl zirconium tris-pivalate is activated with methylalumoxane, then combined with Compound I, then injected in the reactor.
• the combined metal compounds and the activator are combined in ratios of about 1000:1 to about 0.5:1.
• the metal compounds and the activator are combined in a ratio of about 300:1 to about 1 :1, preferably about 150:1 to about 1 : 1 , for boranes, borates, aluminates, etc. the ratio is preferably about 1 : 1 to about 10:1 and for alkyl aluminum compounds (such as diethylaluminum chloride combined with water) the ratio is preferably about 0.5:1 to about 10:1.
• the mixed catalyst composition of the present invention may alternately include the
• Group 15 containing metal compound, as described above, and a conventional-type transition catalyst are examples of metal compounds, as described above, and a conventional-type transition catalyst.
• Conventional-type transition metal catalysts are those traditional Ziegler-Natta, vanadium and Phillips-type catalysts well known in the art. Such as, for example Ziegler- Natta catalysts as described in Ziegler-Natta Catalysts and Polymerizations, John Boor,
• the conventional-type transition metal catalyst compounds that may be used in the present invention include transition metal compounds from Groups 3 to 17, preferably 4 to 12, more preferably 4 to 6 of the Periodic Table of Elements.
• These conventional-type transition metal catalysts may be represented by the formula: MR X , where M is a metal from Groups 3 to 17, preferably Group 4 to 6, more preferably Group 4, most preferably titanium; R is a halogen or a hydrocarbyloxy group; and x is the oxidation state of the metal M.
• R include alkoxy, phenoxy, bromide, chloride and fluoride.
• Non-limiting examples of conventional-type transition metal catalysts where M is titanium include TiCl 4 , TiBr 4 , Ti(OC 2 H 5 ) 3 Cl, Ti(OC 2 H 5 )Cl 3 , Ti(OC 4 H 9 ) 3 Cl, Ti(OC 3 H 7 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Br 2 , TiCl 3 »l/3AlCl 3 and Ti(OC ⁇ 2 H 25 )Cl 3 .
• the prefe ⁇ ed conventional-type vanadium catalyst compounds are VOCl 3 , VC1 4 and VOCl 2 -OR where R is a hydrocarbon radical, preferably a Cj to Cio aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates.
• R is a hydrocarbon radical, preferably a Cj to Cio aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and van
• chromium catalyst compounds often refe ⁇ ed to as Phillips-type catalysts, suitable for use in the present invention include CrO , chromocene, silyl chromate, chromyl chloride (CrO 2 Cl 2 ), chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc) ), and the like.
• CrO chromocene
• silyl chromate chromyl chloride
• CrO 2 Cl 2 chromium-2-ethyl-hexanoate
• Cr(AcAc) chromium acetylacetonate
• Non-limiting examples are disclosed in U.S. Patent Nos. 3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which are herein fully incorporated by reference.
• catalysts may include cationic catalysts such as A1C1 3 , and other cobalt, iron, nickel and palladium catalysts well known in the art. See for example U.S. Patent Nos. 3,487,112, 4,472,559, 4,182,814 and 4,689,437 all of which are incorporated herein by reference.
• these conventional-type transition metal catalyst compounds excluding some conventional-type chromium catalyst compounds are activated with one or more of the conventional-type cocatalysts described below.
• conventional type transition metal catalysts can be activated using the activators described above in this patent specification as appreciated by one in the art.
• Conventional-type cocatalyst compounds for the above conventional-type transition metal catalyst compounds may be represented by the formula M 3 M 4 v X 2 c R 3 b - c , wherein M 3 is a metal from Group 1 to 3 and 12 to 13 of the Periodic Table of Elements; M 4 is a metal of Group 1 of the Periodic Table of Elements; v is a number from 0 to 1; each X 2 is any halogen; c is a number from 0 to 3; each R 3 is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and wherein b minus c is at least 1.
• M 3 R 3 k is a Group IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals
• each R 3 may be any monovalent hydrocarbon radical.
• Non- limiting examples of conventional-type organometallic cocatalyst compounds useful with the conventional-type catalyst compounds described above include methyllithium, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium, di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminum alkyls, such as tri-hexyl- aluminum, triethylaluminum, trimethylaluminum, and tri-isobutylaluminum.
• Non-limiting examples of such conventional-type cocatalyst compounds include di- isobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethylberyllium chloride, ethylcalcium bromide, di-isobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, dichloroboron hydride, di-bromo- aluminum hydride and bromocadmium hydride.
• the above described Group 15 containing catalysts and/or the mixed catalyst system including the Group 15 containing catalyst compound and the bulky ligand metallocene catalyst compound, or conventional catalyst compound, may be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below.
• the Group 15 containing catalyst or the mixed catalyst system of the invention is in a supported form, for example deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
• the bulky ligand metallocene catalyst supported on a separate carrier than the Group 15 containing catalyst particularly for use in a reactor system where one supported catalyst system is used in one reactor to produce the high molecular weight component and the other supported catalyst system is used in another reactor to produce the low molecular component.
• support or “carrier” are used interchangeably and are any support material, preferably a porous support material, including inorganic or organic support materials.
• inorganic support materials include inorganic oxides and inorganic chlorides.
• Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds or any other organic or inorganic support material and the like, or mixtures thereof.
• resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds or any other organic or inorganic support material and the like, or mixtures thereof.
• the prefe ⁇ ed carriers are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides.
• the prefe ⁇ ed supports include silica, alumina, silica-alumina, and mixtures thereof.
• Other useful supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite (EP-Bl 0 511 665), phyllosihcate, zeolites, tale, clays and the like.
• combinations of these support materials may be used, for example, silica-chromium, silica- alumina, silica-titania and the like.
• Additional support materials may include those porous acrylic polymers described in EP 0 767 184 Bl, which is incorporated herein by reference.
• the carrier most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 100 rn-2/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 5 to about 500 ⁇ m. More preferably, the surface area of the carrier is in the range of from about 50 to about 500 m ⁇ /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ m.
• the surface area of the carrier is in the range is from about 100 to about 400 m ⁇ /g, pore volume from about 0.8 to about 5.0 cc/g and average particle size is from about 5 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 450A.
• the Group 15 containing catalyst compounds and/or the mixed catalyst system including the bulky ligand metallocene catalyst compounds may contain a polymer bound ligand as described in U.S. Patent Nos. 5,473,202 and 5,770,755, which is herein fully incorporated by reference; the Group 15 containing catalyst compounds and/or the bulky ligand metallocene catalyst compounds of the invention may be spray dried as described in U.S. Patent No.
• the support used with the Group 15 containing metal catalyst compounds and/or the bulky ligand metallocene catalyst compounds of the invention may be functionalized as described in European publication EP- A-0 802 203, which is herein fully incorporated by reference, or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880, which is herein fully incorporated by reference.
• the invention provides for a Group 15 containing catalyst system and/or a mixed system including the bulky ligand metallocene catalyst compounds, which include a surface modifier that is used in the preparation of the supported catalyst system as described in PCT publication WO 96/11960, which is herein fully incorporated by reference.
• the catalyst systems of the invention can be prepared in the presence of an olefin, for example hexene-1.
• the Group 15 containing hafnium catalyst system and the mixed system including the bulky ligand metallocene catalyst compound can be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Application Serial No. 09/113,216, filed July 10, 1998.
• a carboxylic acid salt of a metal ester for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Application Serial No. 09/113,216, filed July 10, 1998.
• a method for producing a supported Group 15 containing catalyst system and or the bulky ligand metallocene catalyst system is described below and is described in U.S. Application Serial Nos. 265,533, filed June 24, 1994 and 265,532, filed June 24, 1994 and PCT publications WO 96/00245 and WO 96/00243 both published January 4, 1996, all of which are herein fully incorporated by reference.
• This procedure is used either with the Group 15 containing catalyst compounds together with or separately from the bulky ligand metallocene catalyst compounds.
• the catalyst compound or compounds are slurried in a liquid to form a solution and a separate solution is formed containing an activator and a liquid.
• the liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the catalyst compound or compounds and/or activator of the invention.
• the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.
• the catalyst compound or compounds and activator solutions are mixed together and added to a porous support such that the total volume of the catalyst compound or compounds solution and the activator solution or the catalyst compound or compounds solution 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; prefe ⁇ ed ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
• the loading of the total of Group 15 containing compound and the bulky ligand metallocene catalyst compound in ⁇ mmol per gram (g) of finished supported catalyst is about 40 ⁇ mmol per gram, preferably about 38 ⁇ mmol/g.
• the loading of the total of Group 15 containing compound and the bulky ligand metallocene catalyst compound in ⁇ mmol per gram of finished supported catalyst is less than 30 ⁇ mmol per gram, preferably less than 25 ⁇ mmol/g, more preferably less than 20 ⁇ mmol/gram.
• the R group in formula (VII) above, or ligand may be covalently bonded to a support material, preferably a metal/metalloid oxide or polymeric support.
• Lewis base-containing support materials or substrates will react with the Lewis acid activators to form a support bonded Lewis acid compound, a supported activator, where one R group of R n Al(ArHal) 3 . n is covalently bonded to the support material.
• the support material is silica
• the Lewis base hydroxyl groups of the silica is where this method of bonding at one of the aluminum coordination sites occurs.
• the support material is a metal or metalloid oxide, preferably having surface hydroxyl groups exhibiting a pK a equal to or less than that observed for amorphous silica, i.e., pK a less than or equal to about 11.
• the covalently bound anionic activator the Lewis acid
• the Lewis acid is believed to form initially a dative complex with a silanol group, for example of silica (which acts as a Lewis base), thus forming a formally dipolar (zwitterionic) Bronsted acid structure bound to the metal/metalloid of the metal oxide support. Thereafter, the proton of the Bronsted acid appears to protonate an R-group of the Lewis acid, abstracting it, at which time the Lewis acid becomes covalently bonded to the oxygen atom.
• a silanol group for example of silica (which acts as a Lewis base)
• R' is a suitable support material or substrate, for example, silica or hydroxyl group-containing polymeric support.
• R' is a suitable support material or substrate, for example, silica or hydroxyl group-containing polymeric support.
• Any support material that contain surface hydroxyl groups are suitable for use in this particular supporting method.
• Other support material include glass beads.
• these compositions may additionally contain oxides of other metals, such as those of Al, K, Mg, Na, Si, Ti and Zr and should preferably be treated by thermal and/or chemical means to remove water and free oxygen.
• thermal and/or chemical means to remove water and free oxygen.
• treatment is in a vacuum in a heated oven, in a heated fluidized bed or with dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, etc.
• the level of treatment should be such that as much retained moisture and oxygen as is possible is removed, but that a chemically significant amount of hydroxyl functionality is retained.
• calcining at up to 800 °C or more up to a point prior to decomposition of the support material, for several hours is permissible, and if higher loading of supported anionic activator is desired, lower calcining temperatures for lesser times will be suitable.
• the metal oxide is silica
• loadings to achieve from less than 0.1 mmol to 3.0 mmol activator/g Si ⁇ 2 are typically suitable and can be achieved, for example, by varying the temperature of calcining from 200 to 800+ °C. See Zhuralev, et al, Langmuir 1987, Vol. 3, 316 where co ⁇ elation between calcining temperature and times and hydroxyl contents of silica's of varying surface areas is described.
• the tailoring of hydroxyl groups available as attachment sites can also be accomplished by the pre-treatment, prior to addition of the Lewis acid, with a less than stoichiometric amount of the chemical dehydrating agents.
• those used will be used sparingly and will be those having a single ligand reactive with the silanol groups (e.g., (CH3)3SiCl), or otherwise hydrolyzable, so as to minimize interference with the reaction of the transition metal catalyst compounds with the bound activator.
• difunctional coupling agents e.g., (CH3)2SiCl2
• Polymeric supports are preferably hydroxyl-functional-group-containing polymeric substrates, but functional groups may be any of the primary alkyl amines, secondary alkyl amines, and others, where the groups are structurally incorporated in a polymeric chain and capable of a acid-base reaction with the Lewis acid such that a ligand filling one coordination site of the aluminum is protonated and replaced by the polymer incorporated functionality. See, for example, the functional group containing polymers of U.S. Patent No. 5,288,677, which is herein incorporated by reference.
• Other supports include silica, alumina, silica-alumina, magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosihcate, zeolites, talc, clays, silica-chromium, silica-alumina, silica-titania, porous acrylic polymers.
• olefin(s), preferably C2 to C30 olefin(s) or alpha-olefin(s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of a supported Group 15 containing metal catalyst and or the bulky ligand metallocene catalyst 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 olefin 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 Group 15 containing metal catalyst compound of the invention and the activator are introduced into a slurry or gas phase reactor in a liquid carrier, preferably in a solution.
• the catalyst and the activator may be fed in separately or together and may be combined immediately before being placed in the reactor or may be contacted for longer periods before being placed in the reactor.
• Prefe ⁇ ed liquid earners include alkanes, preferably pentane, hexane, isopentane, toluene, cyclohexane, isopentane, heptane, octane, isohexane and the like.
• Particularly prefe ⁇ ed liquid carriers include hexane, pentane, isopentane and toluene.
• the catalyst system, the metal compounds and/or the activator are preferably introduced into the reactor in one or more solutions.
• a solution of the activated metal compounds in an alkane such as pentane, hexane, toluene, isopentane or the like is introduced into a gas phase or slurry phase reactor.
• the catalyst system or the components can be introduced into the reactor in a suspension or an emulsion.
• the transition metal compound is contacted with the activator, such as modified methylalumoxane, in a solvent and just before the solution is fed into a gas or slurry phase reactor.
• the activator such as modified methylalumoxane
• a solution of the metal compound is combined with a solution of the activator, allowed to react for a period of time then introduced into the reactor.
• the catalyst and activator are allowed to reactor for at least 1 second, preferably at least 5 minutes even more preferably between 5 and 60 minutes, before being introduced into the reactor.
• the catalyst and activator are typically present at a concentration of 0.0001 to 0.200 mol/1 in the solutions, preferably 0.001 to 0.05 mol/1, more preferably 0.005 to 0.025 mol/1.
• the metal compound and the activator are combined in ratios of about 1000:1 to about 0.5:1.
• the metal compound and the activator are combined in a ratio of about 300: 1 to about 1:1, preferably about 10:1 to about 1 :1, for boranes the ratio is preferably about 1 :1 to about 10:1 and for alkyl aluminum compounds (such as diethylaluminum chloride combined with water) the ratio is preferably about 0.5:1 to about 10:1.
• the catalyst system consists of the transition metal compound (catalyst) and/or the activator (cocatalyst) which are preferably introduced into the reactor in solution.
• Solutions of the metal compounds are prepared by taking the catalyst and dissolving it in any solvent such as an alkane, toluene, xylene, etc.
• the solvent may first be purified in order to remove any poisons which may affect the catalyst activity, including any trace water and/or oxygenated compounds. Purification of the solvent may be accomplished by using activated alumina and activated supported copper catalyst, for example.
• the catalyst is preferably completely dissolved into the solution to form a homogeneous solution. Both catalyst and the activator may be dissolved into the same solvent, if desired. Once the catalysts are in solution, they may be stored until use.
• the catalyst is combined with an activator prior to injection into the reactor. Additionally, other solvents and reactants can be added to the catalyst solutions (on-line or off-line), to the activator (on-line or off-line), or to the activated catalyst or catalysts.
• the catalyst systems of this invention have a productivity of 10,000 grams of polymer per gram of catalyst per hour or more.
• the solution fed catalyst system of this invention described above has excellent operability over a wide range of reactor conditions and resin grades from 0.2 dg/min Flow Index to 3 dg/min Melt Index and 0.950 g/cc to 0.916 g/cc density.
• the catalyst system did not experience any resin agglomeration or sheeting in over 10 days of continuous pilot scale operation.
• This invention also has the benefit of little or no fouling. No sheets, chunks or rubble were observed during or after the polymerization process. There was no trace of polymer build-up on the inside of the reactor walls or in the recycle gas line. Also, there was no increase in the pressure drop across the heat exchanger, cycle gas compressor or gas distribution plate during the entire run.
• the mixed catalyst systems of the invention and/or the activator (cocatalyst) are introduced into the reactor in solution.
• Solutions of the metal compounds are prepared by taking the catalyst and dissolving it in any suitable solvent such as an alkane, toluene, xylene, etc.
• the solvent may first be purified in order to remove any poisons, which may affect the catalyst activity, including any trace water and or oxygenated compounds. Purification of the solvent may be accomplished by using activated alumina and activated supported copper catalyst.
• the catalyst is preferably completely dissolved into the solution to form a homogeneous solution. Both catalysts may be dissolved into the same solvent, if desired. Once the catalysts are in solution, they may be stored indefinitely until use.
• the catalyst is combined with an activator prior to introduction into the reactor.
• other solvents and reactants can be added to the catalyst solutions (on-line or off-line), to the activator (on-line or off-line), or to the activated catalyst or catalysts. See U.S. Patent Nos. 5,317,036 and 5,693,727, EP-A-0 593 083, and WO 97/46599 which are fully incorporated herein by reference, that describe solution feed systems to a reactor. There are many different configurations which are possible to combine the catalysts and activator.
• the catalyst systems, the metal compounds and/or the activator(s) may be introduced into the reactor in one or more solutions.
• the metal compounds may be activated independently, in series or together.
• a solution of the two activated metal compounds in an alkane such as pentane, hexane, toluene, isopentane or the like is introduced into a gas phase or slurry phase reactor.
• the catalysts system or the components can be introduced into the reactor in a suspension or an emulsion.
• the second metal compound is contacted with the activator, such as modified methylalumoxane, in a solvent and just before the solution is fed into a gas, slurry or solution phase reactor.
• a solution of the Group 15 containing metal compound is combined with a solution of the second compound and the activator and then introduced into the reactor.
• A refers to a catalyst or mixture of catalysts
• B refers to a different catalyst or mixture of catalysts.
• the mixtures of catalysts in A and B can be the same catalysts, just in different ratios. Further, it is noted that additional solvents or inert gases may be added at many locations.
• Illustration 1 A and B plus the activator are mixed off-line and then fed to the reactor. Illustration 1 is graphically represented in Figure 1.
• Illustration 2 A and B are mixed off-line. Activator is added in-line and then fed to the reactor. Illustration 2 is graphically represented in Figure 2. Illustration 3: A or B is contacted with the activator (off-line) and then either A or B is added in-line before entering the reactor. Illustration 3 is graphically represented in Figure 3. Illustration 4: A or B is contacted with the activator (on-line) and then either A or B is added in-line before entering the reactor. Illustration 4 is graphically represented in Figure 4. Illustration 5: A and B are each contacted with the activator off-line. Then A and activator and B and activator are contacted in line before entering the reactor. Illustration 5 is graphically represented in Figure 5.
• Illustration 6 A and B are each contacted with the activator in-line. Then A and activator and B and activator are contacted in-line before entering the reactor. (This is a prefe ⁇ ed configuration since the ratio of A to B and the ratio of activator to A and the ratio of activator to B can be controlled independently.). Illustration 6 is graphically represented in Figure 6. Illustration 7: In this example, A or B is contacted with the activator (on-line) while a separate solution of either A or B is contacted with activator off-line. Then both stream of A or B and activator are contacted in-line before entering the reactor. Illustration 7 is graphically represented in Figure 7. Illustration 8: A is contacted on-line with B. Then, an activator is fed to in-line to the A and B mixture. Illustration 8 is graphically represented in Figure 8.
• Illustration 9 A is activated with activator off-line. Then A and activator is contacted online with B. Then, an activator is fed to in-line to the A and B and activator mixture. Illustration 9 is graphically represented in Figure 9.
• a means for mixing and/or creating a certain residence time may be employed.
• a mixing blade or screw may be used to mix the components or a certain length pipe may be used to obtain a desired contact or residence time between the components.
• On-line means the material described is in a pipe, tube, or vessel which is directly or indirectly connected to the reactor system.
• Off-line means the material described is in a pipe, tube, or vessel which is not connected to the reactor system.
• this invention relates to a method to polymerize olefins in a gas-phase reactor wherein at least two catalysts and at least one activator are introduced in the polymerization reactor in a liquid carrier.
• the catalysts and the activator(s) are combined in the liquid carrier before being introduced into the reactor.
• the catalysts are combined in a liquid carrier then introduced into a channeling means connecting to the reactor and thereafter the activator(s) is introduced into the channeling means at the same or different point as the catalysts.
• the catalysts are combined in a liquid carrier and thereafter the activator(s) is introduced into the liquid carrier.
• the liquid ca ⁇ ier containing the catalysts and the activator(s) are placed into an apparatus for introducing the liquid carrier into the reactor.
• the catalysts and liquid carrier are introduced into the apparatus before the activator is introduced into the apparatus.
• composition comprising the liquid carrier comprises a liquid stream flowing or sprayed into the reactor.
• At least one catalyst, at least one activator and the liquid carrier are placed into an apparatus for introduction into the reactor wherein additional catalyst(s) is/are introduced into the apparatus after the first catalyst and activator are introduced into the apparatus.
• the catalyst composition, catalyst systems, mixed catalyst systems, supported catalyst systems or solution feed catalyst systems of the invention described above are suitable for use in any polymerization process, including solution, gas or slurry processes or a combination thereof.
• the polymerization process is preferably a gas or slurry phase process and more preferably utilizes a single reactor, and most preferably a single gas phase reactor.
• this invention is directed toward the polymerization or copolymerization reactions involving the polymerization of one or more monomers 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-l, hexene-1, octene-1, decene-1, 3-methyl-pentene-l, 3,5,5- trimethyl-hexene-1 and cyclic olefins or a combination thereof.
• Other monomers can include vinyl monomers, diolefms such as dienes, polyenes, norbornene, norbornadiene monomers.
• a copolymer of ethylene is produced, where the comonomer is at least one alpha- olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from 4 to 8 carbon atoms and most preferably from 4 to 7 carbon atoms.
• the geminally disubstituted olefins disclosed in WO 98/37109 may be polymerized or copolymerized using the invention herein described.
• ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer.
• the prefe ⁇ ed comonomers are a combination of alpha-olefin monomers having 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, optionally with at least one diene monomer.
• the prefe ⁇ ed 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 3 to 8 carbon atoms, preferably 4 to 7 carbon atoms.
• the comonomers are butene-1, 4-methyl- pentene-l, hexene-1 and octene-1, the most prefe ⁇ ed being hexene-1 and/or butene-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 10 psig (69 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 100 psig (690 kPa) to about 400 psig (2759 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 75°C to 110°C, and most preferably in the range of from about 85°C to about 110°C. Altering the polymerization temperature can also be used as a tool to alter the final polymer product properties.
• the productivity of the catalyst or catalyst system is influenced by the main monomer partial pressure.
• the prefe ⁇ ed mole percent of the main monomer, ethylene or propylene, preferably ethylene, is from about 25 to 90 mole percent and the monomer partial pressure is in the range of from about 75 psia (517 kPa) to about 300 psia (2069 kPa), which are typical conditions in a gas phase polymerization process.
• the ethylene partial pressure is about 220 to 240 psi (1517 to 1653 kPa).
• the molar ratio of hexene to ethylene ins the reactor is 0.03:1 to 0.08:1.
• the reactor utilized in the present invention and the process of the invention produce greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
• 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 prefe ⁇ ed polymerization technique of the invention is refe ⁇ ed 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.
• the prefe ⁇ ed temperature in the particle form process is within the range of about 185°F (85°C) to about 230°F (110°C).
• Two prefe ⁇ ed polymerization methods for the slurry process are those employing a loop reactor and those utilizing a plurality of sti ⁇ ed reactors in series, parallel, or combinations thereof.
• Non-limiting examples of slurry processes include continuous loop or sti ⁇ ed tank processes.
• other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference.
• the slurry process is ca ⁇ ied out continuously in a loop reactor.
• the catalyst as a solution, as a suspension, as an emulsion, as a slurry in isobutane or as a dry free flowing powder is injected regularly to the reactor loop, which is itself filled with circulating slurry of growing polymer particles in a diluent of isobutane containing monomer and comonomer.
• Hydrogen optionally, may be added as a molecular weight control.
• the reactor is maintained at pressure of about 525 psig to 625 psig (3620 kPa to 4309 kPa) and at a temperature in the range of about 140 °F to about 220 °F (about 60 °C to about 104 °C) depending on the desired polymer density.
• Reaction heat is removed through the loop wall since much of the reactor is in the form of a double-jacketed pipe.
• the slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isobutane diluent and all unreacted monomer and comonomers.
• the resulting hydrocarbon free powder is then compounded for use in various applications.
• the reactor used in the slurry process of the invention is capable of producing greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr).
• the slurry reactor used in the process of the invention is producing greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (1 1,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
• the total reactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig (5516 kPa), preferably 450 psig ( 3103 kPa) to about 700 psig (4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).
• the concentration of ethylene in the reactor liquid medium is in the range of from about 1 to 10 weight percent, preferably from about 2 to about 7 weight percent, more preferably from about 2.5 to about 6 weight percent, most preferably from about 3 to about 6 weight percent.
• a prefe ⁇ ed 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 diethyl aluminum chloride, dibutyl zinc and the like.
• any scavengers such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
• a slurry of an aluminum distearate in mineral oil is introduced into the reactor, separately or with the first and/or second metal complex and/or with an activator, from the metal compounds and/or the activators. More information on using aluminum stearate type additives may be found in U.S. Application Serial No. 09/113,261 filed July 10, 1998, which is incorporated by reference herein.
• the second metal compound and Group 15 metal compound of the catalyst system are introduced to the reactor in series, it is preferably that the second metal compound is added and/or activated first and that the Group 15 metal compound is added and/or activated second.
• the residence time of the catalyst composition is between about 3 to about 6 hours and preferably between about 3.5 and about 5 hours.
• the mole ratio of comonomer to ethylene, C x /C 2 , where C x is the amount of comonomer and C 2 is the amount of ethylene is between about 0.001 to 0.0100 and more preferably between about 0.002 to 0.008.
• the melt index ( and other properties) of the polymer produced may be changed by manipulating hydrogen concentration in the polymerization system by: 1) changing the amount of the first catalyst in the polymerization system, and/or
• the hydrogen concentration in the reactor is about 100 to 5000 ppm, preferably 200 to 2000 ppm, more preferably 250 to 1900 ppm, more preferably 300 to 1800 ppm, and more preferably 350 to 1700 ppm, more preferably 400 to 1600 ppm, more preferably 500 to 1500 ppm, more preferably 500 to 1400 ppm, more preferably 500 to 1200 ppm, more preferably 600 to 1200 ppm, preferably 700 to 1100 ppm, and more preferably 800 to 1000 ppm.
• the hydrogen concentration in the reactor being inversely proportional to the polymer's weight average molecular weight (M w ). Polymer of the Invention
• the new polymers produced by the process of the present invention may be used in a wide variety of products and end use applications.
• the new polymers include polyethylene, and bimodal polyethylene produced in a single reactor by the mixed catalyst system of the invention In addition to bimodal polymers, it is not beyond the scope of the present application for the mixed system to produce a unimodal or multi-modal polymer.
• the Group 15 containing metal compound when used alone, produces a high weight average molecular weight M w polymer (such as for example above 100,000, preferably above 150,000, preferably above 200,000, preferably above 250,000, more preferably above 300,000).
• the second metal compound when used alone, produces a low molecular weight polymer (such as for example below 80,000, preferably below 70,000, preferably below 60,000, more preferably below 50,000, more preferably below 40,000, more preferably below 30,000, more preferably below 20,000 and above 5,000, more preferably below 20,000 and above 10,000).
• the polyolefins, particularly polyethylenes, produced by the present invention have a density of 0.88 to 0.97g/cm 3 (As measured by ASTM 2839).
• polyethylenes having a density of 0.910 to 0.965g/cm , more preferably 0.915 to 0.960 g/cm , and even more preferably 0.920 to 0.955 g/cm 3 can be produced.
• a density of 0.915 to 0.940 g/cm 3 would be prefe ⁇ ed, in other embodiments densities of 0.930 to 0.970 g/cm 3 are prefe ⁇ ed.
• the polyolefin recovered typically has a melt index I (as measured by ASTM D-1238, Condition E at 190°C ) of about 0.01 to lOOOdg/min or less.
• the polyolefin is ethylene homopolymer or copolymer.
• a melt index of lOdg/min or less is prefe ⁇ ed.
• a melt index of 1 dg/min or less is prefe ⁇ ed.
• Polyethylene having a I 2 between 0.01 and lOdg/min is prefe ⁇ ed.
• the polymer produced herein has an I 2 ⁇ (as measured by ASTM-D-1238-F, at 190 °C) of 0.1 to lOdg/min, preferably 0.2 to 7.5dg/min, preferably 2.0dg/min or less, preferably 1.5dg/min or less, preferably 1.2dg/min or less, more preferably between 0.5 and LOdg/min, more preferably between 0.6 and 0.8dg/min.
• the polymers of the invention have a melt flow index "MIR" of I 2 ⁇ /I 2 of 80 or more, preferably 90 or more, preferably 100 or more, preferably 125 or more.
• the polymer has an I 21 (as measured by ASTM 1238, condition F, at 190 °C)(sometimes refe ⁇ ed to as Flow Index) of 2.0dg/min or less, preferably
• the catalyst composition described above is used to make a polyethylene having a density of between 0.94 and 0.970 g/cm (as measured by ASTM D 2839) and an I 2 of 0.5 or less g/lOmin or less
• the catalyst composition described above is used to make a polyethylene having an I j of less than 10 and a density of between about 0.940 and 0.950g/cm or an I 21 of less than 20 and a density of about 0.945g/cm or less.
• the polymer of the invention is made into a pipe by methods known in the art.
• the polymers of the invention have a I 2 ⁇ of from about 2 to about 10 dg/min and preferably from about 2 to about 8dg/min.
• the pipe of the invention satisfies ISO qualifications.
• the catalyst composition of the present invention is used to make polyethylene pipe able to withstand at least 50 years at an ambient temperature of 20°C, using water as the internal test medium and either water or air as the outside environment (Hydro static (hoop) stress as measured by ISO TR 9080).
• the polymer has a notch tensile test (resistance to slow crack growth) result of greater than 150hours at 3.0MPa, preferably greater than 500hours at 3.0MPa and more preferably greater than 600 hours at 3.0mPa. (as measured by ASTM- F1473).
• the catalyst composition of the present invention is used to make polyethylene pipe having a predicted S-4 T c for 110mm pipe of less than -5°C, preferably of less than -15°C and more preferably less than -40°C (ISO DIS 13477/ASTM F1589).
• the polymer has an extrusion rate of greater than about 171bs/hour/inch of die circumference and preferably greater than about 201bs/hour/inch of die circumference and more preferably greater than about 221bs/hour/inch of die circumference
• the polyolefins of the invention can be made into films, molded articles (including pipes), sheets, wire and cable coating and the like.
• the films may be formed by any of the conventional techniques known in the art including extrusion, co-extrusion, lamination, blowing and casting.
• the film may be obtained by the flat film or tubular process which may be followed by orientation in a uniaxial direction or in two mutually perpendicular directions in the plane of the film to the same or different extents. Orientation may be to the same extent in both directions or may be to different extents.
• Particularly prefe ⁇ ed methods to form the polymers into films include extrusion or coextrusion on a blown or cast film line.
• the polymer of the invention is made into a film by methods known in the art.
• the polymers of the invention have a I ⁇ of from about 2 to about 50dg/min, preferably from about 2 to about 30dg/min, even more preferably from about 2 to about 20dg/min, still more preferably about 5 to about 15 dg/min and yet more preferably from about 5 to about lOdg/min.
• the polymer has an MD Tear of .5mil (13 ⁇ ) film of between about 5g/mil and 25g/mil preferably, between about 15g/mil and 25g/mil, and more preferably between about 20g/mil and 25g/mil.
• the films produced may further contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, polymer processing aids, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents.
• additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, polymer processing aids, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents.
• Prefe ⁇ ed additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, BaSO 4 , diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, hydrocarbon resins, glass beads and the like.
• the additives may be present in the typically effective amounts well known in the art, such as
• the polymer of the invention is made into a molded article by methods known in the art, for example, by blow molding and injection-stretch molding.
• the polymers of the invention have a I 2 ⁇ of from about 20dg/min to about 50dg/min and preferably from about 35dg/min to about 45dg/min.
• the polymers of the invention including those described above, have an ash content less than lOOppm, more preferably less than 75ppm, and even more preferably less than 50ppm is produced.
• the ash contains negligibly small levels of titanium as measured by Inductively Coupled Plasma/ Atomic Emission Spectroscopy (ICPAES) as is well known in the art.
• ICPAES Inductively Coupled Plasma/ Atomic Emission Spectroscopy
• the polymers of the invention contain a nitrogen containing ligand detectable by High Resolution Mass Spectroscopy (HRMS) as is well known in the art.
• HRMS High Resolution Mass Spectroscopy
• M n and M w were measured by gel permeation chromatography on a waters 150°C GPC instrument equipped with differential refraction index detectors.
• the GPC columns were calibrated by running a series of molecular weight standards and the molecular weights were calculated using Mark Houwink coefficients for the polymer in question.
• Density was measured according to ASTM D 1505.
• CDBI composition distribution breadth index
• MI Melt Index
• I 21 was measured according to ASTM D-1238, Condition F, at 190°C.
• Melt Index Ratio is the ratio of I 21 over I 2 as determined by ASTM D-1238. Weight % comonomer was measured by proton NMR.
• MD and TD Elmendorf Tear were measured according to ASTM D 1922.
• MD and TD 1% Secant modulus were measured according to ASTM D 882.
• MD and TD tensile strength and ultimate tensile strength were measured according to ASTM D 882.
• MD and TD elongation and ultimate elongation were measured according to ASTM D 412.
• Haze was measured according to ASTM 1003-95, Condition A.
• ESCORENETM LL3002.32 is a linear low density ethylene-hexene copolymer produced in a single gas phase reactor using a Ziegler-Natta catalyst available from Exxon Chemical Company in Houston, Texas, having a density of 0.918 g/cc, an I 2 of 2 dg/min and having a CDBI ( composition distribution breadth index) of less than 65.
• EXCEEDTM ECD 125 is a linear low density ethylene-hexene copolymer produced in a single gas phase reactor using a metallocene catalyst available from Exxon Chemical Company in Houston, Texas, having a density of about 0.91 g/cc, an MI of 1.5 g/10 min.
• ESCORENETM LL3001.63 is a linear low density ethylene-hexene copolymer produced in a single gas phase reactor using a Ziegler-Natta catalyst available from Exxon Chemical Company in Houston, Texas, having a density of 0.918 g/cc, an MI of 1.0 g/10 min.
• EXCEED TM350D60 is a linear low density ethylene-hexene copolymer produced in a single gas phase reactor using a metallocene catalyst available from Exxon Chemical Company in Houston, Texas, having a density of 0.918 g/cc, an MI of 1.0 g/lOmin and.
• PPH pounds per hour.
• mPPH millipounds per hour, “ppmw” is parts per million by weight.
• MD Machine Direction
• TD Transverse Direction.
• Example Section I utilize of a mixed catalyst system which includes a Group 15 containing metal catalyst and a bulky ligand Metallocene Catalyst.
• Example Section I Mixed Catalyst Systems Including Group 15 Containing Metal Catalyst and Bulky Ligand Metallocene Catalyst
• Indenyl zirconium tris pivalate a bulky ligand metallocene compound, also represented by formula VI, can be prepared by performing the following general reactions:
• An ethylene-hexene copolymer was produced in a 14-inch (35.6cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18.1 kg/hr)
• hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.27 kg/hr)
• hydrogen was fed to the reactor at a rate of 5 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 27 PPH.
• the reactor was equipped with a plenum having about 1,900 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor, as described in detail in U.S. Patent No. 5,693,727 which is incorporated herein by reference.
• a tapered catalyst injection nozzle having a 0.041 inch (0.10 cm) hole size was positioned in the plenum gas flow.
• a solution of 1 wt % of Catalyst A in toluene and cocatalyst (MMAO- 3 A, 1 wt % Aluminum) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO -3 A is modified methyl alumoxane in heptane, commercially available from Akzo Chemicals, Inc.
• MMAO to catalyst was controlled so that the Al:Zr molar ratio was 400:1. Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size. A unimodal polymer having nominal 0.28 dg/min (I 21 ) and 0.935 g/cc (density) properties was obtained. A residual zirconium of 1.63 ppmw was calculated based on a reactor mass balance.
• An ethylene- hexene copolymer was produced in a 14-inch (35.6cm) pilot plant scale gas phase reactor operating at 80° C and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 37 pounds per hour (19.8 kg/hr)
• hexene was fed to the reactor at a rate of about 0.4 pounds per hour (0.18 kg/hr)
• hydrogen was fed to the reactor at a rate of 12 mPPH.
• Ethylene was fed to maintain 180 psi (1.2 MPa) ethylene partial pressure in the reactor.
• the production rate was about 25 PPH.
• the reactor was equipped with a plenum having about 1,030 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas- phase reactor.
• a tapered catalyst injection nozzle having a 0.055 inch (0.14cm) hole size was positioned in the plenum gas flow.
• a solution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2 lb/hr (0.09kg/hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes.
• the Catalyst B and hexene mixture were mixed with cocatalyst (MMAO- 3A, 1 wt % Aluminum) in a line for about 40 minutes.
• An ethylene-hexene copolymer was produced in a 14-inch (35.6cm) pilot plant scale gas phase reactor operating at 80° C and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger.
• Ethylene was fed to the reactor at a rate of about 53 pounds per hour (24 kg/hr)
• hexene was fed to the reactor at a rate of about 0.5 pounds per hour (0.22 kg/hr)
• hydrogen was fed to the reactor at a rate of 9 mPPH.
• Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor.
• the production rate was about 25 PPH.
• the reactor was equipped with a plenum having about 990 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.
• a tapered catalyst injection nozzle having a 0.055 inch (0.12) hole size was positioned in the plenum gas flow.
• a solution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2 lb/hr (0.09 kg/hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes.
• the Catalyst B and hexene mixture were mixed with cocatalyst (MMAO- 3 A, 1 wt % Aluminum) in a line for about 20-25 minutes.
• a lwt % Catalyst A in toluene solution was activated with cocatalyst (MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes.
• the two independently activated solutions were combined into a single process line for about 4 minutes.
• the quantity of Catalyst A catalyst was about 40-45 mol% of the total solution fed.
• isopentane and nitrogen were added to control particle size.
• the total system was passed through the injection nozzle into the fluidized bed.
• MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was 300: 1.
• Example Section I - Example 4 A bimodal polymer was produced which was 0.045 g/lOmin melt index and 7.48 g/lOmin flow index. The density was 0.9496 g/cc. A residual zirconium of 1.7 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.
• Example Section I - Example 4 A bimodal polymer was produced which was 0.045 g/lOmin melt index and 7.48 g/lOmin flow index. The density was 0.9496 g/cc. A residual zirconium of 1.7 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I. Example Section I - Example 4:
• An ethylene-hexene copolymer was produced in a 14-inch (35.6cm) pilot plant scale gas phase reactor operating at 85° C and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 50 pounds per hour (22.7 kg/hr), some of the hexene was fed to the reactor at a rate of about 0.7 pounds per hour (0.32 kg/hr) and hydrogen was fed to the reactor at a rate of 11 mPPH.
• Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor. The production rate was about 29 PPH.
• the reactor was equipped with a plenum having about 970 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.
• a tapered catalyst injection nozzle having a 0.055 inch (0.14cm) hole size was positioned in the plenum gas flow.
• a solution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2 lb/hr (0.09 kg/hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes.
• Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 20-25 minutes.
• cocatalyst MMAO-3A, 1 wt % Aluminum
• a separate activating stainless steel tube a lwt % Catalyst A in toluene solution was activated with cocatalyst
• MMAO-3A 1 wt % Aluminum
• the two independently activated solutions were combined into a single process line for about 4 minutes.
• the quantity of Catalyst A catalyst was about 40-45 mol% of the total solution fed.
• isopentane and nitrogen were added to control particle size.
• the total system was passed through the injection nozzle into the fluidized bed.
• MMAO to catalyst was controlled so that the Al:Zr molar ratio was 300: 1.
• a bimodal polymer was produced which was 0.054 g/lOmin melt index and 7.94 g/lOmin flow index. The density was 0.948 g/cc.
• a residual zirconium of 1.1 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.
• An ethylene-hexene copolymer was produced in a 14-inch (35.6cm) pilot plant scale gas phase reactor operating at 85° C and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 60 pounds per hour (27.2 kg/hr)
• hexene was fed to the reactor at a rate of about 0.8 pounds per hour (0.36 kg/hr)
• hydrogen was fed to the reactor at a rate of 13 mPPH.
• Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor.
• the production rate was about 34 PPH.
• the reactor was equipped with a plenum having about 960 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas- phase reactor.
• a tapered catalyst injection nozzle having a 0.055 inch (0.14cm) was positioned in the plenum gas flow.
• a solution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2 lb/hr (0.09 kg/hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes.
• the Catalyst B and hexene mixture were mixed with cocatalyst (MMAO- 3 A, 1 wt % Aluminum) in a line for about 20-25 minutes.
• a lwt % Catalyst A in toluene solution was activated with cocatalyst (MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes.
• the two independently activated solutions were combined into a single process line for about 4 minutes.
• the quantity of Catalyst A catalyst was about 40-45 mol% of the total solution fed.
• isopentane and nitrogen were added to control particle size.
• the total system was passed through the injection nozzle into the fluidized bed.
• MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was 300: 1.
• a bimodal polymer was produced which was 0.077 g/lOmin melt index and 12.7 g/lOmin flow index. The density was 0.9487 g/cc. A residual zirconium of 0.9 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.
• An ethylene-hexene copolymer was produced in a 14-inch (35.6cm) pilot plant scale gas phase reactor operating at 85° C and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 60 pounds per hour (27.2 kg/hr)
• hexene was fed to the reactor at a rate of about 0.8 pounds per hour (0.36 kg/hr)
• hydrogen was fed to the reactor at a rate of 13 mPPH.
• Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor.
• the production rate was about 34 PPH.
• the reactor was equipped with a plenum having about 1,100 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas- phase reactor.
• a tapered catalyst injection nozzle having a 0.055 inch (0.14cm) was positioned in the plenum gas flow.
• a solution of 1 wt % Catalyst B in hexane catalyst was mixed with 0.2 lb/hr (0.09 kg/hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes.
• Catalyst B and hexene mixture were mixed with cocatalyst (MMAO- 3A, 1 wt % Aluminum) in a line for about 10-15 minutes, lwt % Catalyst A in toluene solution was added to the activated Catalyst B solution for about 5 minutes before being sprayed into the reactor.
• the quantity of Catalyst A catalyst was about 40-45 mol% of the total solution fed.
• isopentane and nitrogen were added to control particle size.
• the total system was passed through the injection nozzle into the fluidized bed.
• MMAO to catalyst ratio was controlled so that the final Al:Zr molar ratio was 300: 1.
• a bimodal polymer was produced which was 0.136 g/lOmin melt index and 38.1 g/lOmin flow index. The density was 0.9488g/cc. A residual zirconium of 0.5 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.
• An ethylene-hexene copolymer was produced in a 14-inch (35.6cm)pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger.
• Ethylene was fed to the reactor at a rate of about 42 pounds per hour (19.1 kg hr), hexene was fed to the reactor at a rate of about 0.8 pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13 mPPH.
• Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor.
• the production rate was about 32 PPH.
• the reactor was equipped with a plenum having about 2010 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas- phase reactor.
• a tapered catalyst injection nozzle having a 0.055 inch (0.14cm) was positioned in the plenum gas flow.
• a solution of 0.25 wt % Catalyst B in hexane catalyst was mixed with 0.1 lb/hr (0.05 kg/hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube.
• the Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 15 minutes.
• Catalyst A in toluene solution was added to the activated Catalyst B solution for about 15 minutes before being sprayed into the reactor.
• the quantity of Catalyst A catalyst was about 65-70 mol% of the total solution fed.
• isopentane and nitrogen were added to control particle size.
• the total system was passed through the injection nozzle into the fluidized bed.
• MMAO to catalyst ratio was controlled so that the final Al:Zr molar ratio was 500.
• a bimodal polymer was produced which was 0.06 g/lOmin melt index and 6.26 g/lOmin flow index. The density was 0.9501 g/cc.
• a residual zirconium of 0.65 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.
• Section I - Comparative Examples 1 and 2 give experimental data on how the single component catalyst system behave.
• Examples 3 and 4 demonstrate the effect of temperature on essentially the same reactor conditions and catalyst feed system. Note that at higher temperature, the M w /M n is lower, as is the MFR.
• Examples 5 and 6 compare the effect of activation scheme for essentially the same reactor conditions and catalyst feed system. Note that in Example 6, the overall activity of the catalyst is better. However, the amount of high molecular weight material produced is lower.
• Examples 6 and 7 demonstrate the ability to control the amount of high molecular weight material produced at essentially similar reactor conditions. Example 7 fed a higher percentage of Catalyst A feed, hence a higher quantity of higher Mw material was produced.
• the extrusion condition were: die- 160 mm triplex, 1.5 mm die gap, 400 ° C die temperature, 48 inches (122 cm) layflat width, target melt temperature- 410°F (210 °C), and extrusion rates- 310 lb/hr (144 kg/hr), 420 lb/hr (191 kg/hr) and 460 lb/hr (209 kg/hr).
• ESCORENETM HD7755.10 ( a conventional series reactor product of Exxon Chemical Company, Houston, Texas) was run at the same conditions as a comparison. All films were conditioned according to 23°C, 50% humidity for 40 hours. The data are reported in Table IA. Table IA
• MD Machine Direction
• TD Transverse Direction
• UT Str Ultimate Tensile strength
• ESCORENE HD7755.10 is a polyethylene polymer available from Exxon Chemical Company, Houston, Texas, having an I 2 ⁇ of 7.5, and MIR of 125, an M w of 180,000, a density of 0.95 g/cc, produced using a dual reactor system.
• extrusion conditions were: 400 ° F (204° C) die temperature, output rate- 100 lb/hr (46kg/hr).
• a typical set temperature profile was: 380 o F/400 o F/400 o F/400 o F/400 o F/400 o F/410 o F/410 o F (193 o C/204 o C/204 o C/204 o C/204°C/
• the FLH (frost line height) of blown bubble was maintained at 36 inches (91.4cm) and 40 inches (101.6cm), respectively for 1.0 mil (25 ⁇ m) and 0.5 mil (12.5 ⁇ m) film.
• the extrusion head pressure and motor load exhibited slightly higher than ESCORENETM HD7755.10 ( a conventional series reactor product of Exxon Chemical Company in Mt Belvue Texas) at the same extrusion conditions.
• the resultant film properties are reported in Table IB. All the film samples were conditioned at to 23°C, 50% humidity for 40 hours.
• Dart impact strength of 0.5 mil (12.5 ⁇ m) film exhibited 380g, which exceeded that of ESCORENETM HD7755.10 which showed 330g.
• MD machine direction
• TD transverse direction
• Compound I could be dissolved in a solvent, preferably toluene to form the desired weight % solution then used in combination with other catalyst systems.
• Catalyst A could be used as a 0.50 weight % solution in toluene and Catalyst B could be used as a 0.25 weight % solution in hexane at molar ratios of B to A of about 0.7 when the two are activated separately then mixed together (parallel activation) or at molar ratios of B to A of 2.2 to 1.5 when A is activated then B is added (sequential activation).
• a particle lean zone can be created by a 50,000 lb/hr flow of cycle gas through 6 inch pipe.
• the catalyst can be atomized w/ a spray nozzle using nitrogen atomizing gas.
• the activator preferably MMAO 3 A can be used at 7 weight % al in isopentane , hexane or heptane at feed rate sufficient to give an Al/Zr ratio of 100 to 300.
• Catalyst A is mixed on-line with MMAO 3 A then Catalyst B is added on line, then the mixture is introduced into the reactor.
• Catalyst A is mixed on-line with MMAO 3A and Catalyst B is mixed on line with MMAO 3 A thereafter the two activated catalysts are mixed on-line then introduced into the reactor.
• the examples in Example Section II, below, utilize a catalyst system which includes a Group 15 containing metal catalyst having benzyl leaving groups.
• Polymerization was performed in the slurry-phase in a 1 -liter autoclave reactor equipped with a mechanical sti ⁇ er, an external water jacket for temperature control, a septum inlet and vent line, and a regulated supply of dry nitrogen and ethylene.
• the reactor was dried and degassed at 160°C.
• Isobutane 400 mL was added as a diluent and 0.7 mL of a 25 weight percent trioctyl aluminum solution in hexane was added as a scavenger using a gas tight syringe.
• the reactor was heated to 90°C.
• Polymerization was performed in the slurry -phase in a 1 -liter autoclave reactor equipped with a mechanical sti ⁇ er, an external water jacket for temperature control, a septum inlet and vent line, and a regulated supply of dry nitrogen and ethylene.
• the reactor was dried and degassed at 160°C.
• Isobutane 400 mL was added as a diluent and 0.7 mL of a 25 weight percent trioctyl aluminum solution in hexane was added as a scavenger using a gas tight syringe.
• the reactor was heated to 90°C.
• the Group 15 containing metal catalyst compound having the substituted hydrocarbon leaving group, preferably the alkyl substituted with an aryl group of the invention has a much higher productivity than the same compound having a halogen.
• Example Section III utilize of a catalyst system which includes a Silica Bound Aluminum activator.
• Example Section III Catalyst System including Silica Bound Aluminum
• Polymerization was performed in the slurry-phase in a 1 -liter autoclave reactor equipped with a mechanical sti ⁇ er, an external water jacket for temperature control, a septum inlet and vent line, and a regulated supply of dry nitrogen and ethylene.
• the reactor was dried and degassed at 160°C.
• Isobutane 400 mL is added as a diluent, 35 mL of 1-hexene, and 0.7 mL of a 25 weight percent trioctyl aluminum in hexane is added as a scavenger using a gas tight syringe.
• the reactor was heated to 60°C.
• Example Section IV utilizes a solution feed of a Group 15 containing metal catalyst.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr)
• hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.3 kg/hr)
• hydrogen was fed to the reactor at a rate of 5 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 27 PPH.
• the reactor was equipped with a plenum having about 1,900 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041inch (0.11 cm) hole size was position in the plenum gas flow.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger.
• Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr)
• hexene was fed to the reactor at a rate of about 3.5 pounds per hour (1.6 kg/hr)
• hydrogen was fed to the reactor at a rate of 25 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 20 PPH.
• the reactor was equipped with a plenum having about 1,900 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041inch (0.11 cm) hole size was position in the plenum gas flow.
• a solution of 1 wt % Catalyst A in toluene, 0.22 PPH of 1-hexene and co-catalyst (MMAO-3A, 4 wt % Aluminum in isopentane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 746:1.
• Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 1.2 dg/min (I 2 ), 29.7 dg/min (I 21 ), 23.9 I 21 /I 2 ratio and 0.9165 g/cc properties was obtained.
• a residual zirconium of 0.89 ppmw was calculated based on a reactor mass balance.
• Example Section IV - Example 3 An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 105° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr), hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 6 mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 24 PPH. The reactor was equipped with a plenum having about 1,600 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) hole size was position in the plenum gas flow.
• a solution of 1.5 wt % Catalyst A in toluene, and cocatalyst (MMAO-3A, 1.8 wt % Aluminum in 25 % heptane / 75% hexane solution) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 320:1.
• Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 0.67 dg/min (I ⁇ ) and 0.9358 g/cc properties was obtained.
• a residual zirconium of 2.33 ppmw was calculated based on a reactor mass balance.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 36 pounds per hour (16.3 kg/hr)
• hexene was fed to the reactor at a rate of about 3.5 pounds per hour (1.6 kg/hr)
• hydrogen was fed to the reactor at a rate of 28 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 18 PPH.
• the reactor was equipped with a plenum having about 1,900 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041 inch (0.11 cm) hole size was position in the plenum gas flow.
• a solution of 1 wt % Catalyst A in toluene, 0.22 PPH of 1-hexene and cocatalyst (MMAO-3A, 4 wt % Aluminum in isopentane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 925:1.
• Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 1.7 dg/min (I 2 ), 41.7 dg/min (I 2 ⁇ ), 24.1 I 21 /I 2 and 0.917 g/cc properties was obtained.
• a residual zirconium of 0.94 ppmw was calculated based on a reactor mass balance.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr)
• hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.3 kg/hr)
• hydrogen was fed to the reactor at a rate of 3.5 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH.
• the production rate was about 22 PPH.
• the reactor was equipped with a plenum having about 1,500 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041 inch (0.11 cm) hole size was position in the plenum gas flow.
• a solution of 1 wt % Catalyst A in toluene and cocatalyst (MMAO-3 A, 1 wt % Aluminum in hexane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 450: 1. Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• Example Section IV - Example 6 A unimodal polymer having nominal 0.10 dg/min (I 2 ⁇ ) and 0.931 g/cc properties was obtained. A residual zirconium of 1.36 ppmw was calculated based on a reactor mass balance.
• Example Section IV - Example 6 A unimodal polymer having nominal 0.10 dg/min (I 2 ⁇ ) and 0.931 g/cc properties was obtained. A residual zirconium of 1.36 ppmw was calculated based on a reactor mass balance.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger.
• Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr)
• hexene was fed to the reactor at a rate of about 0.5 pounds per hour (0.23 kg/hr)
• hydrogen was fed to the reactor at a rate of 4 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 20 PPH.
• the reactor was equipped with a plenum having about 2,050 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041 inch (0.11 cm) hole size was position in the plenum gas flow.
• a solution of 1 wt % Catalyst A in toluene and cocatalyst (MMAO-3A, 4 wt % Aluminum in isopentane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 1550:1.
• Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 0.36 dg/min (I 21 ) and 0.943 g/cc properties was obtained.
• a residual zirconium of 2.5 ppmw was calculated based on a reactor mass balance.
• Example Section IV - Example 7 An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr), hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 12 mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 20 PPH. The reactor was equipped with a plenum having about 2,050 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041 inch (0.11 cm) hole size was position in the plenum gas flow.
• a solution of 1 wt % Catalyst A in toluene and cocatalyst (MMAO-3 A, 4 wt % Aluminum in isopentane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 868: 1. Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 3.5 dg/min (I 2 ⁇ ), 0.115 dg/min (I 2 ), 30.2 I 21 /I 2 ratio and 0.949 g/cc properties was obtained.
• a residual zirconium of 2.5 ppmw was calculated based on a reactor mass balance.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger.
• Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18 kg/hr)
• hexene was fed to the reactor at a rate of about 1.1 pounds per hour
• hydrogen was fed to the reactor at a rate of 12 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 25 PPH.
• the reactor was equipped with a plenum having about 1,900 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.041 inch (0.11 cm) hole size was position in the plenum gas flow.
• a solution of 1 wt % Catalyst A in toluene and cocatalyst (MMAO-3 A, 4 wt % Aluminum in isopentane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 842:1. Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 41.2 dg/min (I 1 ), 1.22 dg/min (I 2 ), 33.8 121/12 ratio and 0.940 g/cc properties was obtained.
• a residual zirconium of 2.77 ppmw was calculated based on a reactor mass balance.
• An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 90° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger
• Ethylene was fed to the reactor at a rate of about 48 pounds per hour
• hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.3 kg/hr)
• hydrogen was fed to the reactor at a rate of 10 mPPH.
• Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 23 PPH
• the reactor was equipped with a plenum having about 1,600 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.055 inch (1.4 cm) hole size was position in the plenum gas flow.
• a solution of 1.5 wt % Catalyst A in toluene, and cocatalyst (MMAO-3 A, 1.8 wt % Aluminum in 25%heptane/75%hexane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 265:1.
• Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size.
• a unimodal polymer having nominal 0.3 dg/min (I 1 ) and 0.933 g/cc properties was obtained.
• a residual zirconium of 2.38 ppmw was calculated based on a reactor mass balance.
• Example Section IV - Example 10 An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 95° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger Ethylene was fed to the reactor at a rate of about 45 pounds per hour, hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.3 kg/hr) and hydrogen was fed to the reactor at a rate of 6 mPPH. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 25 PPH. The reactor was equipped with a plenum having about 1,600 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.055 inch (1.4 cm) hole size was position in the plenum gas flow.
• a solution of 1.5 wt % Catalyst A in toluene, and cocatalyst (MMAO-3 A, 1.8 wt % Aluminum in 25 %heptane/75% hexane) were mixed in line prior to passing through the injection nozzle into the fluidized bed.
• MMAO and catalyst were controlled so that the Al:Zr molar ratio was 350:1.
• Example Section IV Examples 1 to 10 are summarized in Table II.
• ESCORENETM HD7755.10 (a conventional series reactor product of Exxon Chemical Company in Mt. Belvue Texas) was run at the same conditions as a comparison. All films were conditioned according to 23°C, 50%> humidity for 40 hours. The data are presented in Tables III and IV.
• Example Section V utilizes solution feed of a mixed catalyst system which includes a Group 15 containing metal catalyst and a bulky ligand Metallocene Catalyst.
• Example Section V Solution Feed of Mixed Catalyst Systems Including Group 15 Containing Metal Catalyst and Bulky Ligand Metallocene Catalyst
• Catalyst 1 For purposes of this Example Section V, Catalyst 1 is indenyl zirconium tris pivalate, a bulky ligand metallocene-type compound, prepared as described in Example Section 1.
• Catalyst 2 the [(2,4,6- Me3C6H2)NHCH2CH2]2NH ligand (Ligand I) and the ⁇ [(2,4,6- Me3C6H2)NCH2CH2]2 H ⁇ Zr(CH2Ph)2 (Compound I) were prepared as described in Example Section I.
• An ethylene hexene copolymer was produced in a 14-inch pilot plant scale gas phase reactor operating at 85° C and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger
• the reactor was equipped with a plenum having about 1,600 PPH of recycle gas flow.
• the plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor. See US Patent 5,693,727.
• a tapered catalyst injection nozzle having a 0.055 inch (1.4 cm) hole size was position in the plenum gas flow.
• ethylene pressure was about 220 psia (1.5 MPa)
• 1-hexene concentration was about 0.3 mol %
• hydrogen concentration was about 0.12 mol %>.
• Catalyst 2 was dissolved in a 0.5 wt% solution in toluene and was fed to reactor at 12 cc/hr.
• MMAO-3 A, 1 wt % Aluminum) co-catalyst was mixed with the Catalyst 2 in the feed line prior to the reactor at a molar ratio of 400:1 Al/Zr.
• the production rate was about 24 lb/hr(10.9kg/hr).
• 5.0 lbs/hr (2.3 kg/hr) Nitrogen and 0.1 lbs/hr(0.05 kg/hr) 1- hexene and 0.2 lb/hr (0.09 kg/hr) isopentane were also fed to the injection nozzle.
• the polymer had a flow index of 0.31 and a density of 0.935 g/cc. After this was established, the catalyst feed rate was reduced to 6 cc/hr of catalyst 2 and a 0.125 wt%> Catalyst 1 in hexane solution feed was added to the injection line at 13 cc/hr. The entire order of addition was the hexene and the MMAO mixed with the Catalyst 1 , Catalyst 2 solution was added, then isopentane and nitrogen. The Al/Zr for the entire system was about 500.
• the bimodal polymer had a nominal 12.9 dg/min (I 21 ), a 130 MFR(melt flow ratio I 2 ⁇ /I 2 )and 0.953 g/cc density.
• the resin average particle size was 0.0479 inched (0.12 cm).
• a residual zirconium of 0.7 ppmw was measured by x-ray fluorescence.

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