WO2011071900A2 - Procédés de réduction d'une charge statique d'un catalyseur et procédés d'utilisation du catalyseur pour produire des polyoléfines - Google Patents

Procédés de réduction d'une charge statique d'un catalyseur et procédés d'utilisation du catalyseur pour produire des polyoléfines Download PDF

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WO2011071900A2
WO2011071900A2 PCT/US2010/059256 US2010059256W WO2011071900A2 WO 2011071900 A2 WO2011071900 A2 WO 2011071900A2 US 2010059256 W US2010059256 W US 2010059256W WO 2011071900 A2 WO2011071900 A2 WO 2011071900A2
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catalyst
reactor
polymerization
polymer
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PCT/US2010/059256
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WO2011071900A3 (fr
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Maria A. Apecetche
Maria Pollard
Robert O. Hagerty
Michael D. Awe
Kevin J. Cann
Jose F. Cevallos-Candau
F. David Hussein
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Univation Technologies, Llc
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Priority to CN2010800557570A priority Critical patent/CN102712701A/zh
Priority to BR112012013675A priority patent/BR112012013675A2/pt
Priority to US13/512,943 priority patent/US8722820B2/en
Priority to RU2012128353/04A priority patent/RU2012128353A/ru
Priority to EP10790503A priority patent/EP2510019A2/fr
Publication of WO2011071900A2 publication Critical patent/WO2011071900A2/fr
Publication of WO2011071900A3 publication Critical patent/WO2011071900A3/fr
Priority to US14/222,944 priority patent/US20140200317A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/02—Anti-static agent incorporated into the catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • An interplay of forces may result in particles agglomerating with adjacent particles, and may lead to sheeting.
  • the particles stick together, forming agglomerated particles that affect fluid flow and may be difficult to remove from the system.
  • tacky particles gather on a surface of the reactor system, such as the wall of the reactor vessel, forming a sheet of polymer particles. Progressive cycles in this process may eventually result in the growth of the sheet and its falling into the fluid bed. These sheets can interrupt fluidization, circulation of gas and withdrawal of the product from the reactor, and may require a reactor shutdown for removal.
  • the pre-polymerized catalyst can also include a polymer coupled to the catalyst.
  • the pre-polymerized catalyst may have a ratio by weight of primary monomer in the polymer to the catalyst is less than about 30: 1, or less than about 20: 1.
  • the overall charge of the pre-polymerized catalyst may be less than about 0.3 ⁇ /g, or less than about 0.25 ⁇ /g.
  • entrainment static is one of the key drivers for dome sheeting with various catalysts, particularly metallocene-based catalysts.
  • Entrainment static is generally characterized by the charging of resin and catalyst particles by frictional contact with the walls of the reactor vessel and different parts of the recycle system. High entrainment static is believed to begin immediately with the introduction of catalyst during start-up, and develop during an initial low grade reaction that is followed by rapid activation to full productivity. During this induction period the entrainment static can cause sheeting and other operability issues.
  • the entrainment static causes the catalyst to migrate to the walls of the fluidized bed reactor vessel.
  • the heat that is generated at the wall is not carried away by the gas moving through the fluidized bed. Therefore, the polymer particles being formed along the wall of the reactor vessel become tacky and stick to the wall of the reactor vessel, thereby initiating sheeting.
  • the static charge is also believed to be responsible, at least in part, for sheeting and chunking in the dome section of the reactor vessel.
  • the amount of sheeting and particle agglomeration (also referred to as "chunking") is reduced. Additionally, the pre- polymerized catalyst may exhibit a longer shelf life, as exhibited by a slow decay of the pre- polymer. The longer shelf life may be particularly evident for metallocene catalysts being pre- polymerized with ethylene.
  • the catalyst can be pre-polymerized using any suitable polymerization or "pre- polymerization” process. It has been surprisingly discovered that use of continuity additives can be reduced or avoided when using the pre-polymerized catalyst in gas phase fluidized bed polymerization reactors. For example, gas phase fluidized bed polymerization using the pre- polymerized catalyst can be carried out in the substantial absence of continuity additives. As used herein, the terms "substantial absence of continuity additives" and “substantially free of continuity additives” refer to a polymerization process in which no continuity additive is intentionally added thereto.
  • substantially absence and “substantially free of can also refer to a concentration of continuity additive within the gas phase fluidized bed reactor is less than 5 ppmw, less than 4 ppmw, less than 3 ppmw, less than 2 ppmw, less than 1 ppmw, less than 0.5 ppmw, or less than 0.1 ppmw, based on the polymer production rate.
  • the pre-polymerized catalyst and one or more olefins can be introduced to a gas phase fluidized bed reactor ("polymerization reactor” or “reactor") operated at conditions sufficient to produce one or more polyolefin products.
  • the reactor can be substantially free of any continuity additives during polymerization from an initial start-up of the reactor through shutdown of the reactor.
  • a continuity additive can be introduced during initial start-up of the reactor, but after polymerization begins and continues for a period of time, introduction of the continuity additive can be stopped and polymerization can continue substantially free of any continuity additives.
  • the reactor can be started without any continuity additives being introduced thereto, but after carrying out polymerization for a period of time a continuity additive can then be introduced to the reactor.
  • the pre-polymerized catalyst can include a catalyst that includes a catalytically active material on a support, and a polymer (also referred to as a "pre-polymer") coupled to the catalyst, e.g., formed thereon during pre-polymerization of the catalyst.
  • a catalyst that includes a catalytically active material on a support, and a polymer (also referred to as a "pre-polymer”) coupled to the catalyst, e.g., formed thereon during pre-polymerization of the catalyst.
  • Illustrative catalysts may include metallocene catalysts, Ziegler-Natta catalysts, and chromium- and titanium-based catalysts.
  • Metallocene compounds are generally described throughout in, for example, 1 & 2 METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000); G. G. Hlatky in 181 COORDINATION CHEM. REV. 243-296 (1999) and in particular, for use in the synthesis of polyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000).
  • the Cp ligands are one or more rings or ring system(s), at least a portion of which includes ⁇ -bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues.
  • the ring(s) or ring system(s) typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and, in a particular example, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum, and combinations thereof, where carbon makes up at least 50% of the ring members.
  • Such ligands include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9- phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2- 9]anthrene, thiophenoindenyl, thiopheno fluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7- tetrahydroindenyl, or "H 4 Ind”), substituted versions thereof (as discussed and described in more detail below), and heterocyclic versions thereof.
  • H 4 Ind substituted versions thereof
  • the metal atom "M" of the metallocene compound can be selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms in one example; and selected from the group consisting of Groups 3 through 10 atoms in another example, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet another example; and selected from the group consisting of Groups 4, 5, and 6 atoms in yet another example, and Ti, Zr, Hf atoms in yet another example, and Hf in yet a more particular example.
  • the oxidation state of the metal atom "M” can range from 0 to +7 in one example; and in a more particular example, can be +1, +2, +3, +4 or +5; and in yet a more particular example can be +2, +3 or +4.
  • the groups bound to the metal atom "M” are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated.
  • the Cp ligand(s) forms at least one chemical bond with the metal atom M to form the "metallocene catalyst compound.”
  • the Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.
  • the one or more metallocene compounds can be represented by the formula (I):
  • each Cp A and Cp B of formula (I) can be unsubstituted or substituted with any one or combination of substituent groups R.
  • substituent groups R as used in structure (I) as well as ring substituents in structures Va-d, discussed and described below, include groups selected from the group consisting of hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof.
  • alkyl substituents R associated with formulas (I) through (Va-d) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example, tertiary-butyl, isopropyl, and the like.
  • radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl, hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like, and halocarbyl-substituted organometalloid radicals, including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron, for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, as well as Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methyl
  • substituent groups R include, but are not limited to, olefins such as olefinically unsaturated substituents including vinyl-terminated ligands such as, for example, 3-butenyl, 2-propenyl, 5-hexenyl and the like.
  • olefins such as olefinically unsaturated substituents including vinyl-terminated ligands such as, for example, 3-butenyl, 2-propenyl, 5-hexenyl and the like.
  • at least two R groups are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof.
  • a substituent group R such as 1-butanyl can form a bonding association to the element M.
  • Each X in the formula (I) above and for the formula/structures (II) through (Va-d) below is independently selected from the group consisting of: any leaving group, in one example; halogen ions, hydrides, Ci to C 12 alkyls, C2 to C 12 alkenyls, Ce to C 12 aryls, C7 to C2 0 alkylaryls, Ci to C12 alkoxys, Ce to Ci6 aryloxys, C7 to Cs alkylaryloxys, Ci to C 12 fluoroalkyls, Ce to C 12 fluoroaryls, and Ci to C 12 heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular example; hydride, halogen ions, Ci to Ce alkyls, C2 to Ce alkenyls, C7 to Ci 8 alkylaryls, Ci to Ce alkoxys, Ce to C 14 aryloxys, C7 to Ci 6 alkylaryloxys, Ci to Ce al
  • X groups include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., — C 6 F5 (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF3C(0)CT), hydrides, halogen ions and combinations thereof.
  • X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N- methylanilide), dimethylamide, dimethylphosphide radicals and the like.
  • two or more X's form a part of a fused ring or ring system.
  • bridged metallocenes These bridged compounds represented by formula (II) are known as "bridged metallocenes.”
  • the elements Cp A , Cp B , M, X and n in structure (II) are as defined above for formula (I); where each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp.
  • the bridging group (A) can include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, tin atom, and combinations thereof; where the heteroatom can also be Ci to Ci 2 alkyl or aryl substituted to satisfy neutral valency.
  • the bridging group (A) can also include substituent groups R as defined above (for formula (I)) including halogen radicals and iron.
  • the bridging group (A) can include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1 ,2-dimethylethylene, 1 ,2-diphenylethylene, 1 , 1,2,2- tetramethylethylene, dimethyls ilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t- butylphenyl)silyl, di(p-tolyl)silyl, di
  • the bridging group (A) can also be cyclic, having, for example, 4 to 10 ring members; in a more particular example, bridging group (A) can have 5 to 7 ring members.
  • the ring members can be selected from the elements mentioned above, and, in a particular example, can be selected from one or more of B, C, Si, Ge, N and O.
  • Non-limiting examples of ring structures which can be present as, or as part of, the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O. In another example, one or two carbon atoms can be replaced by at least one of Si and Ge.
  • the bonding arrangement between the ring and the Cp groups can be either cis-, trans-, or a combination thereof.
  • the cyclic bridging groups (A) can be saturated or unsaturated and/or can carry one or more substituents and/or can be fused to one or more other ring structures. If present, the one or more substituents can be selected from the group consisting of hydrocarbyl (e.g., alkyl, such as methyl) and halogen (e.g., F, CI).
  • hydrocarbyl e.g., alkyl, such as methyl
  • halogen e.g., F, CI
  • the one or more Cp groups to which the above cyclic bridging moieties can optionally be fused can be saturated or unsaturated, and are selected from the group consisting of those having 4 to 10, more particularly 5, 6, or 7 ring members (selected from the group consisting of C, N, O, and S in a particular example) such as, for example, cyclopentyl, cyclohexyl and phenyl.
  • these ring structures can themselves be fused such as, for example, in the case of a naphthyl group.
  • these (optionally fused) ring structures can carry one or more substituents.
  • substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms.
  • the metallocene compound can include bridged mono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components).
  • the at least one metallocene catalyst compound can be a bridged "half-sandwich” metallocene represented by the formula (III):
  • Cp A , (A) and Q can form a fused ring system.
  • the X groups of formula (III) are as defined above in formulas (I) and (II).
  • Cp A is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions thereof, and combinations thereof.
  • Q in formula (III), can be a heteroatom-containing ligand in which the bonding atom (the atom that is bonded with the metal M) is selected from the group consisting of Group 15 atoms and Group 16 atoms.
  • the bonding atom can be selected from the group consisting of nitrogen, phosphorus, oxygen, or sulfur atoms.
  • the bonding atom can be selected from the group consisting of nitrogen and oxygen.
  • Illustrative Q groups can include, but are not limited to, alkylamines, arylamines, mercapto compounds, ethoxy compounds, carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene, phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzene other compounds having Group 15 and Group 16 atoms capable of bonding with M.
  • the metallocene compound can be an unbridged "half sandwich” metallocene represented by the formula (IVa):
  • Cp A can be selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, and combinations thereof.
  • Q is selected from the group consisting of ROO , RO— , R(O)— ,— NR— ,— CR 2 — ,— S— ,— NR 2 ,— CR 3 ,— SR,— S1R 3 ,— PR2,— H, and substituted and unsubstituted aryl groups
  • R is selected from the group consisting of Ci to Ce alkyls, Ce to Ci 2 aryls, Ci to Ce alkylamines, Ce to C12 alkylarylamines, Ci to Ce alkoxys, Ce to C 12 aryloxys, and the like.
  • Non-limiting examples of Q include Ci to C 12 carbamates, Ci to C 12 carboxylates (e.g., pivalate), C2 to C
  • W2GZ forms a polydentate ligand unit (e.g., pivalate), where at least one of the W groups form a bond with M, and is defined such that each W is independently selected from the group consisting of— O— ,— NR— ,— CR 2— and— S— ; G is either carbon or silicon; and Z is selected from the group consisting of R,— OR,— NR 2 ,— CR 3 ,— SR,— SiR 3 ,— PR 2 , and hydride, providing that when W is— NR— , then Z is selected from the group consisting of— OR,— NR 2 ,— SR,— S1R 3 ,— PR2; and provided that neutral valency for W is satisfied by Z; and where each R is independently selected from the group consisting of Ci to C 10 heteroatom containing groups, Ci to C 10 alkyls, Ce to C 12 aryls, Ce to C alkylaryls
  • the metallocene compounds discussed and described above include their structural or optical or enantiomeric isomers (racemic mixture), and, in one example, can be a pure enantiomer.
  • a single, bridged, asymmetrically substituted metallocene compound having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene compounds.
  • the "metallocene catalyst” or “metallocene compound” can include any combination of any "example” discussed and described herein.
  • metallocene compounds can include, but are not limited to, metallocenes discussed and described in U.S. Patent Nos.: 7, 179,876; 7, 169,864; 7, 157,531 ; 7, 129,302; 6,995, 109; 6,958,306; 6,884,748; 6,689,847; U.S. Patent Application Publication No. 2007/0055028; and WO Publication Nos. WO 97/22635; WO 00/69922; WO 01/30860; WO 01/30861 ; WO 02/46246; WO 02/50088; WO 04/026921 ; and WO 06/019494.
  • co-catalysts and “activators” are used interchangeably and are defined to be any compound or component which can activate a metallocene compound as defined above, for example, a Lewis acid or a non-coordinating ionic activator or ionizing activator or any other compound that can convert a neutral metallocene catalyst component to a metallocene cation.
  • the activator can be aluminoxane, and/or to also use preferably bulky, compatible ionizing activators, neutral or ionic, such as tri(n-butyl) ammonium tetrakis(pentaflurophenyl) boron or a trisperfluorophenyl boron metalloid precursor which ionize the neutral metallocene compound and stabilize its resulting metallocene cation.
  • neutral or ionic such as tri(n-butyl) ammonium tetrakis(pentaflurophenyl) boron or a trisperfluorophenyl boron metalloid precursor which ionize the neutral metallocene compound and stabilize its resulting metallocene cation.
  • Ionizing compounds can include or contain an active proton, or some other cation associated with but not coordinated or only loosely coordinated to the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European Patent Application Publications EP 0570982A1; EP 0520732A1 ; EP 0495375A1; EP 0426637A2; EP 0500944A1 ; EP 0277003A1; EP 0277004A1 ; U.S. Patent Nos. 5, 153,157; 5,198,401; 5,066,741 ; 5,206, 197; 5,241,025; 5,387,568; 5,384,299; and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994.
  • Combinations of activators are also contemplated, for example, aluminoxanes and ionizing activators in combinations, see for example, WO 94/07928; U.S. Application Serial No. 08/155,313 filed November 19, 1993; and U.S. Patent No. 5,153, 157.
  • Two or more metallocenes can be as described above can be combined to form a catalyst system, see for example, the mixed catalysts discussed and described in U.S. Patent Nos. 5,281,679 and 5,466,649.
  • Chromium catalysts can be obtained by calcining a chromium compound carried on an inorganic oxide carrier in a non-reducing atmosphere to activate it such that at least a portion of the carried chromium atoms is converted to hexavalent chromium atoms (Cr +6 ) commonly referred to in the art as the Phillips catalyst.
  • Suitable chromium catalysts can include di- substituted chromates, such as Cr0 2 (OR) 2 ; where R is triphenylsilane or a tertiary polyalicyclic alkyl.
  • the chromium catalyst system can further include C1O 3 , chromocene, silyl chromate, chromyl chloride (Cr0 2 Cl 2 ), chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc) 3 ), and the like.
  • Ziegler-Natta catalysts are typically based on titanium chlorides, magnesium chlorides and organometallic alkyl aluminum compounds. Illustrative Ziegler-Natta catalysts are disclosed in EP 103 120; EP 102 503; EP 0 231 102; EP 0 703 246; RE 33,683; US 4,302,565; US 5,518,973; US 5,525,678; US 5,288,933; US 5,290,745; US 5,093,415 and US 6,562,905.
  • Such catalysts include those comprising Group 4, 5, or 6 transition metal oxides, alkoxides and halides, or oxides, alkoxides and halide compounds of titanium, zirconium or vanadium; optionally in combination with a magnesium compound, internal and/or external electron donors (alcohols, ethers, siloxanes, etc.), aluminum or boron alkyl and alkyl halides, and inorganic oxide supports.
  • carrier and “support” are used interchangeably and can be any support material, preferably a porous support material, such as for example, talc, inorganic oxides, inorganic chlorides, for example magnesium chloride, and resinous support materials such as polystyrene or polystyrene divinyl benzene polyolefins or polymeric compounds or any other organic or inorganic support material and the like, or mixtures thereof.
  • Preferred support materials can be or include inorganic oxide materials, which include those of Groups 2, 3, 4, 5, 13 or 14 metal oxides.
  • the catalyst support materials can include silica, alumina, silica-alumina, and mixtures thereof.
  • Other inorganic oxides that can be employed either alone or in combination with silica, alumina, or silica-alumina can be magnesia, titania, zirconia, and the like.
  • the catalyst support can have a surface area ranging from a low of about 1 m 2 /g, about
  • the catalyst support can have a pore volume ranging from a low of about 0.01 cmVg, about 0.1 cm /g, about 0.8 cm /g, or about 1 cm /g to a high of about 2 cm /g, about 2.5 cm /g, about 3 cm 3 /g, or about 4 cm 3 /g.
  • the catalyst support can have an average particle size ranging from a low of about 1 ⁇ , about 5 ⁇ , about 10 ⁇ , or about 20 ⁇ to a high of about 50 ⁇ , about 100 ⁇ , about 200 ⁇ , or about 500 ⁇ .
  • the average pore size of the catalyst support can range from about 10 A to about 1,000 A, preferably from about 50 A to about 500 A, and more preferably from about 75 A to about 350 A.
  • a bi-component catalyst system can be used.
  • the term "bi-component catalyst system” refers to catalyst systems having at least two catalyst components, and may indeed include catalyst systems including several different catalyst components.
  • the bi-component catalyst system can include catalyst systems where differing catalysts are present on a single substrate.
  • bi-component catalyst systems can include systems where catalysts are not on a single substrate.
  • Such catalyst systems may include mixtures of catalysts in a common carrier, as well as catalysts independently fed to the reactor system.
  • one or more catalysts can be employed along with a catalyst system having differing catalysts present on a single substrate.
  • a catalyst (used interchangeably herein with catalyst system) can be pre-polymerized under conditions that reduce the overall charge of the catalyst. That is, the pre-polymerized catalyst has an overall charge that is less than the catalyst's charge in its initial state prior to pre- polymerization.
  • a method for pre-polymerizing a supported catalyst can include contacting the catalyst with one or more monomers under conditions that reduce an overall charge of the (pre- polymerized) catalyst to less than about 75%, or less than 60%, or less than 50%, or less than 40%, or less than 35%, or less than 30%, or less than 25%, of the initial charge of the unpre- polymerized supported catalyst.
  • the initial charge of the supported catalyst can be in the range of about 0.300- 0.600 ⁇ /g as noted above, but may be higher or lower. Accordingly, the pre-polymerized catalyst may have a charge of less than about 0.450 ⁇ /g, less than about 0.350 ⁇ /g, less than about 0.300 ⁇ /g, less than about 0.250 ⁇ /g, less than about 0.200 ⁇ /g, or less than about 0.150 ⁇ /g.
  • the catalyst may be pre-polymerized in any pre-polymerization process using any monomer/comonomer wherein the conditions are such that the overall charge of the pre- polymerized catalyst is less than overall charge of the initial catalyst.
  • the pre- polymerization may be conducted at low temperature and low monomer partial pressure, thereby slowing the rate of reaction and allowing more control over the pre-polymerization of the catalyst.
  • the pre-polymerization may be carried out batchwise or continuously in gas, solution, or slurry phase.
  • the illustrative systems and approaches set forth below in the section entitled "Polymerization Process", or variants thereof, may be used to pre-polymerize the catalyst.
  • the supported catalyst system may be pre polymerized using one or more olefins. Any olefin monomer or combination of monomers may be used. Suitable olefins can include, but are not limited to, ethylene, and/or other olefins having from 3 to about 20 carbon atoms, such as C3-C20 a-olefins, C3-C12 a-olefins, or C3-C8 a-olefins.
  • the catalyst is pre-polymerized with ethylene and one or more comonomers.
  • the comonomer may be another olefin having from 3 to 30 carbon atoms. Preferred comonomers are hexene, butene, and octene.
  • the catalyst is pre-polymerized in the presence of ethylene and hexene.
  • the pre-polymer can be the same polymer for which the pre-polymerized catalyst is intended to be used to produce. Alternatively, the pre-polymer can be different from the polymer for which the pre-polymerized catalyst is intended to be used to produce. In one example, the pre-polymer may be polyethylene and the pre-polymerized catalyst can be intended for polyethylene production.
  • the olefin can be pre-polymerized in the presence of the supported catalyst prior to the main polymerization of the olefin.
  • the pre-polymerization is carried out, for example, by polymerizing about 1 to about 1,000 g, preferably about 5 to about 500 g, more preferably about 10 to about 200 g, of the olefin monomer and/or comonomer per gram-atom of the transition metal compound in the supported catalyst.
  • the pre-polymerization temperature may be about -20° to about 70° C, preferably about -10° to about 60° C, more preferably about 0° to about 50° C.
  • the pre-polymerization may be carried out under atmospheric pressure or elevated pressures.
  • the pre-polymerization may be carried out in the presence of a molecular weight controlling agent such as hydrogen.
  • the amount of the molecular weight controlling agent is limited to an amount in which at least a pre-polymer having an intrinsic viscosity, measured in decalin (dl) at 135° C, of at least about 0.2 dl/g, preferably about 0.5 to about 20 dl/g, is produced.
  • the pre-polymerization may be carried out in the absence of a solvent, or in an inert hydrocarbon medium. In view of operability, it is preferred to carry out the preliminary polymerization in an inert hydrocarbon medium.
  • Inert hydrocarbon mediums can include, but are not limited to, isopentane, hexane, cyclohexane, heptanes, benzene, toluene, and the like.
  • the concentration of the supported catalyst in the pre-polymerization reaction may be, for example, about 10 ⁇ 6 to about 1 gram-atom/liter, as the concentration of the metal atom in the supported catalyst.
  • the ratio by weight of the primary monomer in the pre-polymer to the catalyst can be less than about 500: 1 g/g (g monmer in polymer/g catalyst) , less than about 400 g/g, less than about 200 g/g, less than about 100 g/g, less than about 40: 1 g/g, less than about 30: 1 g/g, less than about 20: 1 g/g, less than about 15: 1 g/g, less than about 10: 1 g/g, or less than about 5: 1 g/g.
  • the ratio by weight of the primary monomer in the pre-polymer to the catalyst can range from about 0.1 : 1 g/g to about 35: 1 g/g, from about 0.5: 1 g/g to about 25: 1 g/g, about 1 : 1 g/g to about 20: 1 g/g, or about 2: 1 g/g to about 15: 1 g/g.
  • Polymers can be made in a variety of processes using the catalysts disclosed herein, including but not limited to, gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid phase reactor systems including polymerization reactor systems; gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid phase mass transfer systems; gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid phase mixing systems; gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid phase heating or cooling systems; gas/solid phase and gas/solid/liquid phase drying systems; or any combination thereof.
  • gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid phase reactor systems including polymerization reactor systems; gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid phase mass transfer systems; gas phase, gas/solid phase, liquid/solid phase, gas/liquid phase, and gas/liquid/solid
  • the reactor can form part of a fluidized bed polymerization reactor system.
  • Gas phase polymerization reactions can be carried out in fluidized bed polymerization reactors, and can also be formed in stirred or paddle-type reactor systems (e.g., stirred bed systems) which include solids in a gaseous environment. While the following discussion will feature fluidized bed systems, where the pre-polymerized catalysts have been found to be especially advantageous, it is to be understood that the general concepts relating to the reduction of a catalyst's static charge, which are discussed relevant to the preferred fluidized bed systems, are also adaptable to the stirred or paddle-type reactor systems as well.
  • a fluidized bed generally includes a bed of particles in which the static friction between the particles is disrupted.
  • the fluidized bed system can be an open fluidized bed system or a closed fluidized bed system.
  • An open fluidized bed system can include one or more fluids and one or more types of fluidized solid particles and have one or more fluidized bed surfaces that are exposed to an open uncontrolled atmosphere.
  • an open fluidized bed system can be an open container such as an open-top tank or an open well of a batch reactor or of a parallel batch reactor (e.g., microliter chamber).
  • the fluidized bed system can be a closed fluidized bed system.
  • a closed fluidized bed system can include one or more fluids and one or more types of fluidized particles that are generally bounded by a barrier so that the fluids and particles are constrained.
  • a closed fluidized bed system can include a pipeline (e.g., for particle transport); or a re-circulating fluidized bed system, such as the fluidized bed polymerization reactor system depicted in Figure 1.
  • a closed fluidized bed system can be in fluid communication with an open fluidized bed system.
  • the fluid communication between a closed fluidized bed system and an open fluidized bed system can be isolatable, for example, using one or more valves.
  • Such isolation valves can be configured for unidirectional fluid flow, such as for example, a pressure relief valve or a check valve.
  • the fluidized bed system (whether open or closed) can be defined by manufactured (e.g., man-made) boundaries comprising one or more barriers.
  • the one or more barriers defining manufactured boundaries can generally be made from natural or non-natural materials.
  • the fluidized bed system (whether open or closed) can be a flow system such as a continuous flow system or a semi-continuous flow (e.g., intermittent-flow) system, a batch system, or a semi-batch system (sometimes also referred to as a semi-continuous system).
  • a flow system such as a continuous flow system or a semi-continuous flow (e.g., intermittent-flow) system, a batch system, or a semi-batch system (sometimes also referred to as a semi-continuous system).
  • fluidized bed systems that are flow systems are closed fluidized bed systems.
  • the fluidized bed can be formed by flow of a gaseous fluid in a direction opposite gravity.
  • the frictional drag of the gas on the solid particles can overcome the force of gravity and suspend the particles in a fluidized state referred to as a fluidized bed.
  • the superficial gas velocity through the bed must exceed the minimum flow required for fluidization. Increasing the flow of the fluidizing gas increases the amount of movement of the particles in the bed, and can result in a beneficial or detrimental tumultuous mixing of the particles. Decreasing the flow results in less drag on the particles, ultimately leading to collapse of the bed.
  • Fluidized beds formed by gases flowing in directions other than vertically include particles flowing horizontally through a pipe, particles flowing downwardly e.g., through a downcomer, etc. Fluidized beds can also be formed by vibrating or otherwise agitating the particles. The vibration or agitation can maintain or place the particles in a fluidized state.
  • a conventional fluidized bed polymerization process for producing resins and other types of polymers can be conducted by passing a gaseous stream containing one or more monomers continuously through a fluidized bed reactor under reactive conditions and in the presence of catalyst at a velocity sufficient to maintain the bed of solid particles in a suspended condition.
  • a continuous cycle is employed where the cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization.
  • the hot gaseous stream also containing unreacted gaseous monomer, is continuously withdrawn from the reactor, compressed, cooled, and recycled into the reactor.
  • Product is withdrawn from the reactor and make-up monomer is added to the system, e.g., into the recycle stream or reactor, to replace the polymerized monomer. See for example U.S. Patent Nos.
  • FIG. 1 depicts a flow diagram of an illustrative gas phase polymerization system 100 for making polymers.
  • the polymerization system 100 can include a reactor 101 in fluid communication with one or more discharge tanks 155 (only one shown), compressors 170 (only one shown), and heat exchangers 175 (only one shown).
  • the polymerization system 100 can also include more than one reactor 101 arranged in series, parallel, or configured independent from the other reactors, each reactor having its own associated discharge tanks 155, compressors 170, and heat exchangers 175, or alternatively, sharing any one or more of the associated discharge tanks 155, compressors 170, and heat exchangers 175.
  • the polymerization system 100 will be further described in the context of a single reactor train.
  • the reactor 101 can include a cylindrical section 103, a transition section 105, and a velocity reduction zone or dome 107.
  • the cylindrical section 103 is disposed adjacent the transition section 105.
  • the transition section 105 can expand from a first diameter that corresponds to the diameter of the cylindrical section 103 to a larger diameter adjacent the dome 107.
  • the location or junction at which the cylindrical section 103 connects to the transition section 105 is referred to as the "neck" or the "reactor neck” 104.
  • the dome 107 has a bulbous shape.
  • One or more cycle fluid lines 1 15 and vent lines 1 18 can be in fluid communication with the top head 107.
  • the reactor 101 can include the fluidized bed 1 12 in fluid communication with the top head 107.
  • the fluidized bed 112 includes a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst all fluidized by the continuous flow of polymerizable and modifying gaseous components, including inerts, in the form of make-up feed and recycle fluid through the reaction zone.
  • the superficial gas velocity through the bed must exceed the minimum flow required for fluidization which is typically from about 0.06 m/s (0.2 ft/s) to about 0.15 m/s (0.5 ft/sec) for polyolefins.
  • the superficial gas velocity is at least 0.06 m/s (0.2 ft/s) above the minimum flow for fluidization or from about 0.12 m s (0.4 ft/s) to about 0.21 m s (0.7 ft/s).
  • the superficial gas velocity will not exceed about 1.5 m/s (5.0 ft/s) and is usually no more than about 0.85 m/s (2.8 ft/s).
  • the height to diameter ratio of the cylindrical section 103 can vary in the range of from about 2: 1 to about 5: 1.
  • the range can vary to larger or smaller ratios and depends, at least in part, upon the desired production capacity and/or reactor dimensions.
  • the cross-sectional area of the dome 107 is typically within the range of from about 2 to about 3 multiplied by the cross-sectional area of the cylindrical section 103.
  • the velocity reduction zone or dome 107 has a larger inner diameter than the fluidized bed 112. As the name suggests, the velocity reduction zone 107 slows the velocity of the gas due to the increased cross-sectional area. This reduction in gas velocity allows particles entrained in the upward moving gas to fall back into the bed, allowing primarily only gas to exit overhead of the reactor 101 through the cycle fluid line 115.
  • the cycle fluid recovered via line 115 can contain less than about 10% wt, less than about 8% wt, less than about 5% wt, less than about 4% wt, less than about 3% wt, less than about 2% wt, less than about 1% wt, less than about 0.5% wt, or less than about 0.2% wt of the particles entrained in fluidized bed 1 12.
  • the reactor 101 can be charged with a bed of particulate polymer particles "seedbed" before gas flow is initiated. Such particles help to prevent the formation of localized "hot spots" when catalyst feed is initiated.
  • the seedbed can be the same as the polymer to be formed or different. When different, the seedbed can be withdrawn with the desired newly formed polymer particles as the first product. Eventually, a fluidized bed primarily of desired polymer particles supplants the start-up bed or seedbed.
  • the reactor feed via line 110 can be introduced to the polymerization system 100 at any point.
  • the reactor feed via line 1 10 can be introduced to the cylindrical section 103, the transition section 105, the velocity reduction zone 107, to any point within the cycle fluid line 1 15, or any combination thereof.
  • the reactor feed 1 10 is introduced to the cycle fluid in line 115 before or after the heat exchanger 175.
  • the reactor feed via line 110 is depicted entering the cycle fluid in line 1 15 after the heat exchanger 175.
  • the catalyst feed via line 1 13 can be introduced to the polymerization system 100 at any point.
  • the catalyst feed via line 1 13 is introduced to the fluidized bed 112 within the cylindrical section 103.
  • the cycle fluid via line 115 can be compressed in the compressor 170 and then passed through the heat exchanger 175 where heat can be exchanged between the cycle fluid and a heat transfer medium.
  • a cool or cold heat transfer medium via line 171 can be introduced to the heat exchanger 175 where heat can be transferred from the cycle fluid in line 1 15 to produce a heated heat transfer medium via line 177 and a cooled cycle fluid via line 1 15.
  • the heat exchanger 175 can be used to cool the fluidized bed 112 or heat the fluidized bed 112 depending on the particular operating conditions of the polymerization system 100, e.g. start-up, normal operation, shut down, polymer product transition period, and the like.
  • Illustrative heat transfer mediums can include, but are not limited to, water, air, glycols, or the like. It is also possible to locate the compressor 170 downstream from the heat exchanger 175 or at an intermediate point between a plurality of heat exchangers 175.
  • the heat exchanger 175 can be of any type of heat exchanger. Illustrative heat exchangers can include, but are not limited to, shell and tube, plate and frame, U-tube, and the like.
  • the heat exchanger 175 can be a shell and tube heat exchanger where the cycle fluid via line 1 15 can be introduced to the tube side and the heat transfer medium can be introduced to the shell side of the heat exchanger 175.
  • several heat exchangers can be employed, in series, parallel, or a combination of series and parallel, to lower or increase the temperature of the cycle fluid in stages.
  • the cycle fluid via line 1 15 is returned to the reactor 101 and to the fluidized bed 1 12 through fluid distributor plate ("plate") 119.
  • the plate 1 19 is preferably installed at the inlet to the reactor 101 to prevent polymer particles from settling out and agglomerating into a solid mass and to prevent liquid accumulation at the bottom of the reactor 101 as well to facilitate easy transitions between processes which contain liquid in the cycle stream 1 15 and those which do not and vice versa.
  • the cycle gas via line 115 can be introduced into the reactor 101 through a deflector disposed or located intermediate an end of the reactor 101 and the distributor plate 119. Illustrative deflectors and distributor plates suitable for this purpose can be as discussed and described in U.S. Patent Nos.
  • the catalyst feed via line 1 13 can be introduced to the fluidized bed 1 12 within the reactor 101 through one or more injection nozzles (not shown) in fluid communication with line 113. In another example, the catalyst feed via line 1 13 can be introduced to the cycle fluid in line 1 15 between the reactor 101 and the heat exchanger 175, for example.
  • a continuity additive can be introduced to the polymerization system 100 via an appropriate mechanism such as feed line 130 to cycle line 1 15. In another example, the continuity additive via line 130 can be introduced directly to the fluidized bed 1 12, the cycle line 1 15, or both.
  • Fluid via line 161 can be separated from a polymer product recovered via line 117 from the reactor 101.
  • the fluid can include unreacted monomer(s), hydrogen, ICA(s), and/or inerts.
  • the separated fluid can be introduced to the reactor 101.
  • the separated fluid can be introduced to the recycle line 115 (not shown).
  • the separation of the fluid can be accomplished when fluid and product leave the reactor 101 and enter the product discharge tanks 155 (one is shown) through valve 157, which can be, for example, a ball valve designed to have minimum restriction to flow when opened.
  • Positioned above and below the product discharge tank 155 can be conventional valves 159, 167.
  • the valve 167 allows passage of product therethrough.
  • valve 157 can be opened while valves 159, 167 are in a closed position.
  • Product and fluid enter the product discharge tank 155.
  • Valve 157 is closed and the product is allowed to settle in the product discharge tank 155.
  • Valve 159 is then opened permitting fluid to flow via line 161 from the product discharge tank 155 to the reactor 101.
  • Valve 159 can then be closed and valve 167 can be opened and any product in the product discharge tank 155 can flow into and be recovered via line 168.
  • Valve 167 can then be closed.
  • the product via line 168 can be introduced to a plurality of purge bins or separation units, in series, parallel, or a combination of series and parallel, to further separate gases and/or liquids from the product.
  • the particular timing sequence of the valves 157, 159, 167, can be accomplished by use of conventional programmable controllers which are well known in the art.
  • Another preferred product discharge system which can be alternatively employed is that disclosed and claimed in U.S. Patent No. 4,621,952.
  • Such a system employs at least one (parallel) pair of tanks comprising a settling tank and a transfer tank arranged in series and having the separated gas phase returned from the top of the settling tank to a point in the reactor near the top of the fluidized bed.
  • the reactor 101 can be equipped with one or more vent lines 1 18 to allow venting the bed during start up, normal operation, shut down, transition between polymer products, and the like.
  • the reactor 101 can be free from the use of stirring and/or wall scraping.
  • the cycle line 1 15 and the elements therein (compressor 170, heat exchanger 175) can be smooth surfaced and devoid of unnecessary obstructions so as not to impede the flow of cycle fluid or entrained particles.
  • the conditions for polymerizations vary depending upon the monomers, catalysts, catalyst systems, and equipment availability. The specific conditions are known or readily derivable by those skilled in the art.
  • the temperatures can be within the range of from about -10°C to about 140°C, often about 15°C to about 120°C, and more often about 70°C to about 110°C.
  • Pressures can be within the range of from about 10 kPag to about 10,000 kPag, such as about 500 kPag to about 5,000 kPag, or about 1,000 kPag to about 2,200 kPag, for example. Additional details of polymerization can be found in U.S. Patent No. 6,627,713, for example.
  • Various systems and/or methods can be used to monitor and/or control the degree or level of fouling or agglomeration within the reactor 101.
  • a common technique for monitoring the reactor 101 can include monitoring a stickiness control parameter ("dMRT") such as a reduced melt initiation temperature or "dMIT" value, which can provide an estimate as to the degree of polymer stickiness within the reactor.
  • dMRT stickiness control parameter
  • dMIT reduced melt initiation temperature
  • Moderated startup or restart conditions can include operating the reactor at a dMIT of about 0°C or a dMIT within about +/- 1°C, about +/- 1.5°C, or about +/- 2°C for a period of time when the normal dMIT ranges from about 5°C to about 10°C. Additional details of monitoring a stickiness control parameter can be as discussed and described in U.S. Patent Application Publication No. 2008/0065360 and U.S. Provisional Patent Application No. 60/842,747.
  • Another method for monitoring polymerization can include estimating acoustic emissions within the reactor 101, which can also provide an estimate as to the degree of polymer stickiness within the reactor.
  • Normal or typical acoustic emissions conditions can be modified such that optimal values during, for example, start-up of the polymerization system 100 or a transition between the production different polymer products. Additional details of monitoring a polymerization reactor via acoustic emissions can be as discussed and described in U.S. Publication No. 2007/0060721.
  • Operating the polymerization system 100 in condensed mode can include introducing an inert condensable fluid to the process to increase the cooling capacity of the polymerization system 100.
  • These inert condensable fluids are referred to as induced condensing agents or ICA's.
  • ICA's induced condensing agents
  • gas phase processes can include, for example, series or multistage polymerization processes. Suitable gas phase processes can also include those discussed and described in U.S. Patent Nos. 3,709,853; 4,003,712; 4,01 1,382; 4,302,566; 4,543,399; 4,588,790; 4,882,400; 5,028,670; 5,352,749; 5,405,922; 5,541,270; 5,627,242; 5,665,818; 5,677,375; 6,255,426 and European Patent Nos. EP 0649992B1, EP 0802202B1, EP 0634421B1 ; European Patent Publication Nos. EP 0794200A2; EP 0802202A1, and EP 1806368A2; and Belgian Patent No. 839,380.
  • the polymerization system 100 can be capable of producing greater than 227 kg/hr (500 lbs/hr) to about 90,900 kg/hr (300,000 lbs/hr) or more of polymer product.
  • the reactor system 100 can produce greater than about 455 kg/hr (1000 lbs/hr), more preferably greater than about 4,540 kg/hr (10,000 lbs/hr), even more preferably greater than about 11,300 kg/hr (25,000 lbs/hr), still more preferably greater than about 15,900 kg/hr (35,000 lbs/hr), still even more preferably greater than about 22,700 kg/hr (50,000 lbs/hr) and most preferably greater than about 29,000 kg/hr (65,000 lbs/hr) to greater than 45,500 kg/hr (100,000 lbs/hr) of polymer product.
  • Stirred bed system include beds stirred or otherwise agitated by a member such as a paddle or plunger rotating or moving through the bed (e.g., stirred bed reactor, blender, etc.).
  • a member such as a paddle or plunger rotating or moving through the bed
  • Other types of stirred bed systems can be formed by a rotating drum (e.g., with or without internal baffles to enhance mixing), a vessel moving in a see-saw manner, agitation including ultrasonic vibrations applied to the particles or their container, etc.
  • the reactor may form part of a liquid phase reactor system.
  • a liquid phase polymerization system such as a slurry, suspension or solution reactor system may be used.
  • the reactor vessel typically contains a liquid reaction medium for dissolving and/or suspending the polyolefin.
  • the liquid reaction medium may consist of the bulk liquid monomer or an inert liquid hydrocarbon that is nonreactive under the polymerization conditions employed. Although such an inert liquid hydrocarbon need not function as a solvent for the catalyst composition or the polymer obtained by the process, it usually serves as solvent for the monomers employed in the polymerization.
  • inert liquid hydrocarbons suitable for this purpose are isopentane, hexane, cyclohexane, heptane, benzene, toluene, and the like.
  • Slurry or solution polymerization systems may utilize subatmospheric or superatmospheric pressures and temperatures in the range of about 40° C. to about 300° C.
  • a useful liquid phase polymerization system is described in U.S. Pat. No. 3,324,095.
  • Polymerization conditions generally refer to temperature, pressure, monomer content (including comonomer concentration), catalyst concentration, cocatalyst concentration, activator concentration, etc., that influence the molecular weight of the polymer produced.
  • polymer refers to a macromolecular compound prepared by polymerizing monomers of the same or a different type.
  • the polymer product(s) produced in the reactor can be or include any type of polymer or polymeric material.
  • the polymer product can include homopolymers of olefins (e.g., homopolymers of ethylene), and/or copolymers, terpolymers, and the like of olefins, particularly ethylene or propylene, and at least one other olefin.
  • Illustrative polymers can include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene polymers, polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrile polymers, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more of the above.
  • Suitable polyolefins can include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40 olefins, preferably polymers comprising propylene copolymerized with one or more C3 to C40 olefins, preferably a C3 to C2 0 alpha olefin, more preferably C3 to C 10 alpha-olefins. More preferred polyolefins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C3 to C40 olefin, preferably a C3 to C2 0 alpha olefin, more preferably propylene and or butene.
  • Preferred polymers include homopolymers or copolymers of C2 to C40 olefins, preferably C2 to C2 0 olefins, preferably a copolymer of an alpha-olefin and another olefin or alpha-olefin (herein ethylene is defined to be an alpha-olefin).
  • the polymers can be or include homo polyethylene, homo polypropylene, propylene copolymerized with ethylene and or butene, ethylene copolymerized with one or more of propylene, butene or hexene, and optional dienes.
  • thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene (“VLDPE”), linear low density polyethylene (“LLDPE”), low density polyethylene (“LDPE”), medium density polyethylene (“MDPE”), high density polyethylene (“HDPE”), polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, elastomers such as ethylene propylene rubber, ethylene propylene diene monomer rubber, neoprene, and blends of thermoplastic polymers and elastomers, such as for example, thermoplastic elastomers and rubber toughened plastics.
  • VLDPE very low density polyethylene
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • polypropylene isotactic polypropylene
  • the terms “monomer” and “comonomer” refers to any compound with a polymerizable moiety which is added to a reactor in order to produce a polymer.
  • polyolefin refers to any polymer containing an olefinic monomer.
  • the polymers can be produced from monomers selected from ethylene, propylene, 1- butene, 1 -hexene, 1-pentene, 4-methyl-l-pentene, 1-octene, 1-decene, vinyl-cyclohexene, styrene, ethylidene norbornene, norbornadiene, 1,3 -butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9- decadiene, or a combination thereof.
  • the polymers can be homopolymers of ethylene or copolymers of ethylene with one or more C3-C20 alpha-olefins.
  • copolymers having two monomeric units are possible as well as terpolymers having three monomeric units.
  • Particular examples of such polymers include ethylene/ 1 -butene copolymers, ethylene/ 1 -hexene copolymers, ethylene/ 1-octene copolymers, ethylene/4-methyl- 1-pentene copolymers, ethylene/ 1 -butene/ 1 -hexene terpolymers, ethylene/propylene/ 1 -hexene terpolymers and ethylene/propylene/ 1 -butene terpolymers.
  • the resulting linear low density polyethylene copolymer preferably has at least one other alpha- olefin comonomer having at least four carbon atoms in an amount of at least 1 percent by weight of the polymer. Accordingly, ethylene/propylene copolymers are also contemplated.
  • a series of pre-polymerization experiments using metallocene catalyst and monomers were performed in laboratory and pilot plant-scale slurry reactors.
  • the experiments were generally performed at milder conditions (lower temperature and lower ethylene partial pressure) than those typically used in a polymerization process using the catalyst to produce high volumes of polymer product.
  • the metallocene catalyst used in the experiments was a dimethyls ilane bis(indenyl) zirconium dichloride catalyst supported on silica with a methylaluminoxane (“MAO”) activator.
  • FIG. 2 depicts an illustrative measurement system 200 for measuring a static charge of a material.
  • the measurement system 200 can include a catalyst spool or catalyst container 205, one or more valves (four are shown 203, 204, 206, 207), one or more coiled tubes 215, a Faraday ring or Faraday “can” 220, and one or more electrometers 225.
  • An inert gas, e.g. nitrogen, via line 202 can be introduced to the catalyst spool 205.
  • valves 203 and 204 can be in fluid communication with line 202 to control the addition of the inert gas to the catalyst spool 205.
  • the inert gas can be a high purity gas.
  • high purity nitrogen can include a gas containing about 99 mol%, about 99.9 mol%, about 99.99 mol%, about 99.999 mol%, or about 99.9999 mol% nitrogen.
  • the valves 206, 207 can be controlled such that the inert gas can flush, urge, or otherwise cause catalyst, polymer, or pre- polymerized catalyst, or other material stored in the catalyst spool 205 to flow through the coiled tube 215 and into the Faraday can 220.
  • the inert gas can flush, urge, or otherwise cause catalyst, polymer, or pre- polymerized catalyst, or other material stored in the catalyst spool 205 to flow through the coiled tube 215 and into the Faraday can 220.
  • about 0.1 g of the material in the catalyst spool 205 can be flushed from the catalyst spool 205 and into the coiled tube 215.
  • the coiled tube 215 can have a diameter of about 0.125 inches and a length of about 4 feet, for example.
  • the atmosphere or environment within the Faraday can 220 can be a high purity gas such as nitrogen.
  • the high purity gas via lien 217 can be introduced to the Faraday can 220. Gas from within the Faraday can 220 can be vented via line 222. As such, a continuous flow of high purity gas via line 217 can be introduced to the Faraday can 220 and a continuous flow of gas can be vented via line 222.
  • the electrometer 225 can measure the static charge on the material, e.g. the catalyst, pre-polymerized catalyst, polymer particles, or the like. Several measurements of the static charging developed on the particles were performed under nitrogen flow until no changes were observed. The readings on each sample were then averaged and the static charge was expressed as microcoulomb/gram ⁇ C/g).
  • Example 1 a silica supported dimethylsilane bis(indenyl) zirconium dichloride catalyst with MAO treated with 1-3 wt% aluminum stearate (“MCN-1”) was polymerized in the presence of ethylene monomer.
  • the catalyst was pre-polymerized to achieve pre-polymer loadings of between about 3 gPE/g catalyst to about 10 gPE/g catalyst.
  • the static charge on the pre-polymerized catalyst was then measured with the averaged results of duplicate static charging measurements on the catalyst and its pre-polymers made with and without 1-hexene in a laboratory slurry reactor shown in Table 2.
  • the catalyst feed rate was adjusted to maintain a constant production rate of polymer.
  • the reacting bed of growing polymer particles was maintained in a fluidized state by the continuous flow of the make up feed and recycle gas through the reaction zone.
  • a superficial gas velocity of about 0.6 m/s to about 0.9 m/s was used to achieve this.
  • the reactor was operated at a total pressure of 2,240 kPa.
  • the reactor was operated at a constant reaction temperature of 85°C.
  • the fluidized bed was maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of formation of particulate product.
  • the rate of product formation (the polymer production rate) was in the range of about 15 kg/hr to about 25 kg/hr.
  • the product was removed semi-continuously via a series of valves into a fixed volume chamber. This product was purged to remove entrained hydrocarbons and treated with a small steam of humidified nitrogen to deactivate any trace quantities of residual catalyst.
  • Continuity additives used in Example 3 include: aluminum distearate and an ethoxylated amine type compound (IRGASTAT AS-990).
  • MAO methylaluminoxane
  • the reactor was operated to produce a polymer product having a melt index (I 2 ) of about 0.76 g/10 min and a density of about 0.9205 g/cm 3 at the following reaction conditions: temperature of 85°C, hexene-to-ethylene molar ratio of 0.0094 and 3 ⁇ 4 to ethylene concentration of 13 (ppm ]3 ⁇ 4/ ⁇ 1% ethylene).
  • the melt index (I 2 ) was measured in accordance with ASTM D-1238-E (at 190°C, 2.16 kg weight).
  • the jacket temperature was used to control the temperature to between 43 °C and 47°C.
  • An additional 500 grams of ethylene, beyond that used for the initial pressure build was introduced to the vessel.
  • the amount of ethylene fed to the vessel is limited to the amount of polymer that will fit into a filter that is used to collect the final product at the end of the process.
  • the pre-polymerization was carried out for about 4 hours.
  • the jacket was cooled to 20°C, thereby cooling the formed pre-polymerized catalyst; and unreacted ethylene was then vented off.
  • the vessel was then purged three times with nitrogen from 0 psig to about 40 psig in order to remove ethylene dissolved in the hexane.
  • a pre-polymerized catalyst and hexane mixture remained in the vessel, which was then discharged into a bag filter to collect the pre-polymerized catalyst, with the filtrate hexane collected as a waste stream.
  • a hexane rinse was passed through the vessel and into the filter to remove loose powder from the walls of the vessel and agitator.
  • the bag filter was purged over night (for convenience) with nitrogen to remove residual hexane. Dry pre-polymerized catalyst was recovered the next day by opening the filter in a glove box and removing the catalyst from the filter bag.
  • the total weight of the pre-polymerized catalyst was about 600 g.
  • Example 3 A test was carried out in the above mentioned polymerization reactor under similar conditions as mentioned in Example 3 above. Initially, the reactor was operated using the same catalyst as in Example 3, which contained the continuity additives blended with the catalyst as well as additional continuity additive co-feed. The reactor was then transitioned to operation using the pre-polymerized catalyst prepared without any continuity additive blended with the catalyst and was subjected to pre-polymerization as discussed and described above.
  • gas-phase fluidized bed polymerization substantially free of any continuity additives was carried without the formation of lumps, chunks, sheets, or the like within the reactor.
  • the pre-polymerized catalyst can be used in gas phase fluidized bed reactors for the polymerization of monomer(s) without the need for any continuity additive to be blended with the catalyst and/or co-fed separately to the reactor.
  • the pre-polymerized catalyst produced polymer particles having improved morphology.
  • the polymer particles produced using the pre-polymerized catalyst had a more uniform and larger particle size distribution as compared to the polymer produced using the convention catalyst.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.

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Abstract

L'invention porte sur des catalyseurs et des procédés pour fabriquer et utiliser ceux-ci. Le procédé de fabrication d'un catalyseur peut comprendre la mise en contact d'un catalyseur supporté avec un monomère dans des conditions qui réduisent une charge globale du catalyseur à moins d'environ 75 % d'une charge initiale du catalyseur. Un procédé de polymérisation peut consister à introduire un catalyseur prépolymérisé et une ou plusieurs oléfines dans un réacteur à lit fluidisé à phase gazeuse, à faire fonctionner le réacteur dans des conditions suffisantes pour produire une polyoléfine, la polymérisation étant effectuée en l'absence notable de tous additifs de continuité.
PCT/US2010/059256 2009-12-07 2010-12-07 Procédés de réduction d'une charge statique d'un catalyseur et procédés d'utilisation du catalyseur pour produire des polyoléfines WO2011071900A2 (fr)

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CN2010800557570A CN102712701A (zh) 2009-12-07 2010-12-07 减少催化剂的静电荷的方法和使用该催化剂生产聚烯烃的方法
BR112012013675A BR112012013675A2 (pt) 2009-12-07 2010-12-07 métodos para a produção de carga estática de um catalisador e métodos para o uso do catalisador para produzir poliolefinas
US13/512,943 US8722820B2 (en) 2009-12-07 2010-12-07 Methods for reducing static charge of a catalyst and methods for using the catalyst to produce polyolefins
RU2012128353/04A RU2012128353A (ru) 2009-12-07 2010-12-07 Способы уменьшения статического заряда катализатора и способы применения такого катализатора для производства полиолефинов
EP10790503A EP2510019A2 (fr) 2009-12-07 2010-12-07 Procédés de réduction d'une charge statique d'un catalyseur et procédés d'utilisation du catalyseur pour produire des polyoléfines
US14/222,944 US20140200317A1 (en) 2009-12-07 2014-03-24 Methods for Reducing Static Charge of a Catalyst and Methods for Using the Catalyst to Produce Polyolefins

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2632878C2 (ru) * 2011-12-31 2017-10-11 Юнивейшн Текнолоджиз, Ллк Добавка для повышения сплошности для процессов полимеризации олефинов
WO2022109518A1 (fr) * 2020-11-17 2022-05-27 Exxonmobil Chemical Patents Inc. Procédé de démarrage d'un réacteur en phase gazeuse
CN117567676A (zh) * 2024-01-16 2024-02-20 新疆独山子石油化工有限公司 一种钛系聚乙烯转产茂金属聚乙烯的生产方法

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* Cited by examiner, † Cited by third party
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EP3087108B2 (fr) 2013-12-23 2022-04-20 Ineos Europe AG Procédé
EP3231506B1 (fr) * 2014-12-09 2023-11-01 China Petroleum & Chemical Corporation Appareil de polymérisation d'oléfines et procédé de polymérisation d'oléfines

Citations (104)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324095A (en) 1965-05-14 1967-06-06 Union Carbide Corp Polymerization process
US3709853A (en) 1971-04-29 1973-01-09 Union Carbide Corp Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts
BE839380A (fr) 1975-03-10 1976-09-10 Procede de preparation de copolymeres d'ethylene de faible densite
US4003712A (en) 1970-07-29 1977-01-18 Union Carbide Corporation Fluidized bed reactor
US4302566A (en) 1978-03-31 1981-11-24 Union Carbide Corporation Preparation of ethylene copolymers in fluid bed reactor
US4302565A (en) 1978-03-31 1981-11-24 Union Carbide Corporation Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization
EP0102503A2 (fr) 1982-07-26 1984-03-14 Toyo Stauffer Chemical Co. Ltd. Procédé de préparation d'un composant de catalyseur utilisé pour la polymérisation des alpha-oléfines
EP0103120A2 (fr) 1982-07-26 1984-03-21 Toyo Stauffer Chemical Co. Ltd. Procédé de préparation d'un composant de catalyseur utilisé pour la polymérisation des alpha-oléfines
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
US4621952A (en) 1981-07-28 1986-11-11 Union Carbide Corporation Fluidized bed discharge process
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
EP0231102A2 (fr) 1986-01-24 1987-08-05 Mobil Oil Corporation Composition de catalyseur pour polymérisation d'oléfines
US4701432A (en) 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
EP0277004A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs et procédé d'utilisation
EP0277003A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs, et procédé de polymérisation en utilisant ces catalyseurs
US4874734A (en) 1987-04-03 1989-10-17 Mitsui Petrochemical Industries, Ltd. Process for producing solid catalyst for polymerization of olefins
US4877587A (en) 1984-08-24 1989-10-31 Union Carbide Chemicals And Plastics Company Inc. Fluidized bed polymerization reactors
US4882400A (en) 1987-07-31 1989-11-21 Bp Chemicals Limited Process for gas phase polymerization of olefins in a fluidized bed reactor
US4908463A (en) 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
WO1990003414A1 (fr) 1988-09-30 1990-04-05 Exxon Chemical Patents Inc. Melanges lineaires d'interpolymeres ethyleniques a distribution etroite de leur poids moleculaire et de leur composition
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US4933149A (en) 1984-08-24 1990-06-12 Union Carbide Chemicals And Plastics Company Inc. Fluidized bed polymerization reactors
US4935474A (en) 1983-06-06 1990-06-19 Exxon Research & Engineering Company Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4937299A (en) 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US4952540A (en) 1987-02-14 1990-08-28 Mitsui Petrochemical Industries, Ltd. Finely divided aluminoxane, process for producing same and its use
US4968827A (en) 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
EP0426637A2 (fr) 1989-10-30 1991-05-08 Fina Technology, Inc. Préparation de catalyseurs métallocènes pour la polymérisation d'oléfines
US5028670A (en) 1988-07-15 1991-07-02 Bp Chemicals Limited Process for the gas-phase polymerization of olefins in a fluidized-bed reactor
USRE33683E (en) 1986-01-24 1991-09-03 Mobil Oil Corporation Catalyst composition for polymerizing alpha-olefins
US5066741A (en) 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
US5077255A (en) 1986-09-09 1991-12-31 Exxon Chemical Patents Inc. New supported polymerization catalyst
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
US5093415A (en) 1987-05-19 1992-03-03 Union Carbide Chemicals & Plastics Technology Corporation Process for producing stereoregular polymers having a narrow molecular weight distribution
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
US5124418A (en) 1985-11-15 1992-06-23 Exxon Chemical Patents Inc. Supported polymerization catalyst
EP0495375A2 (fr) 1991-01-16 1992-07-22 The Dow Chemical Company Procédé de préparation de catalyseurs pour polymérisation par addition par oxydation de centres métalliques
EP0500944A1 (fr) 1990-07-24 1992-09-02 MITSUI TOATSU CHEMICALS, Inc. CATALYSEUR POUR POLYMERISATION $g(a)-OLEFINIQUE ET PRODUCTION D'UNE POLY-$g(a)-OLEFINE A L'AIDE DE CE CATALYSEUR
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
EP0520732A1 (fr) 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5204419A (en) 1986-11-20 1993-04-20 Mitsui Petrochemical Industries, Ltd. Process for polymerizing olefins
US5206197A (en) 1991-03-04 1993-04-27 The Dow Chemical Company Catalyst composition for preparation of syndiotactic vinyl aromatic polymers
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
EP0561476A1 (fr) 1992-03-18 1993-09-22 Akzo Nobel N.V. Solution de polyméthylaluminoxane avec stabilisation améliorée de la solution
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
EP0570982A1 (fr) 1992-05-22 1993-11-24 Tosoh Corporation Catalyseurs et procédé de préparation de polymères d'oléfine
US5281679A (en) 1991-11-07 1994-01-25 Exxon Chemical Patents Inc. Catalyst and method of broadening polymer molecular weight distribution and increasing polymer tensile impact strength and products made thereof
US5288933A (en) 1992-04-16 1994-02-22 Union Carbide Chemicals & Plastics Technology Corporation Process for the production of polyethylene
US5290745A (en) 1992-08-10 1994-03-01 Union Carbide Chemicals & Plastics Technology Corporation Process for producing ethylene polymers having reduced hexane extractable content
WO1994007928A1 (fr) 1992-10-02 1994-04-14 The Dow Chemical Company Complexes de catalyseurs supportes et homogenes utilises dans la polymerisation d'olefines
EP0594218A1 (fr) 1986-09-24 1994-04-27 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines
US5308815A (en) 1991-07-26 1994-05-03 Ethyl Corporation Heterogeneous methylaluminoxane catalyst system
WO1994010180A1 (fr) 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5317036A (en) 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
US5352749A (en) 1992-03-19 1994-10-04 Exxon Chemical Patents, Inc. Process for polymerizing monomers in fluidized beds
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5387568A (en) 1989-10-30 1995-02-07 Fina Technology, Inc. Preparation of metallocene catalysts for polymerization of olefins
US5391660A (en) 1992-01-14 1995-02-21 Nippon Oil Company, Limited Process for preparing polyolefines
US5391793A (en) 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes
US5391529A (en) 1993-02-01 1995-02-21 Albemarle Corporation Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene
US5395810A (en) 1991-09-30 1995-03-07 Fina Technology, Inc. Method of making a homogeneous-heterogenous catalyst system for olefin polymerization
US5405922A (en) 1993-04-26 1995-04-11 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5436304A (en) 1992-03-19 1995-07-25 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5453471A (en) 1994-08-02 1995-09-26 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization process
US5462999A (en) 1993-04-26 1995-10-31 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5466649A (en) 1993-10-15 1995-11-14 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
EP0703246A1 (fr) 1993-07-13 1996-03-27 BP Chemicals Limited Procédé de polymérisation d'oléfine avec un catalyseur Ziegler-Natta
US5518973A (en) 1993-10-15 1996-05-21 Exxon Chemical Patents Inc. Titanium trichloride catalyst system for polymerizing olefins
US5525678A (en) 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
US5541270A (en) 1993-05-20 1996-07-30 Bp Chemicals Limited Polymerization process
US5616661A (en) 1995-03-31 1997-04-01 Union Carbide Chemicals & Plastics Technology Corporation Process for controlling particle growth during production of sticky polymers
US5627242A (en) 1996-03-28 1997-05-06 Union Carbide Chemicals & Plastics Technology Corporation Process for controlling gas phase fluidized bed polymerization reactor
WO1997022635A1 (fr) 1995-12-19 1997-06-26 Exxon Chemical Patents Inc. Procede de polymerisation d'olefine a haute temperature
EP0649992B1 (fr) 1993-10-23 1997-07-30 WABCO GmbH Moteur de frein à disque
US5665818A (en) 1996-03-05 1997-09-09 Union Carbide Chemicals & Plastics Technology Corporation High activity staged reactor process
EP0634421B1 (fr) 1993-07-13 1997-10-08 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfine en phase gazeuse
US5677375A (en) 1995-07-21 1997-10-14 Union Carbide Chemicals & Plastics Technology Corporation Process for producing an in situ polyethylene blend
US6069213A (en) 1997-12-16 2000-05-30 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst system
WO2000069922A2 (fr) 1999-05-17 2000-11-23 Univation Technologies, Llc Procede de polymerisation
WO2001030861A1 (fr) 1999-10-22 2001-05-03 Univation Technologies, Llc Compositions catalytiques, procedes de polymerisation et polymeres fabriques a partir de ces compositions
WO2001030860A1 (fr) 1999-10-22 2001-05-03 Univation Technologies, Llc Systemes catalyseurs et leur utilisation dans un procede de polymerisation
US6255426B1 (en) 1997-04-01 2001-07-03 Exxon Chemical Patents, Inc. Easy processing linear low density polyethylene
WO2002046246A2 (fr) 2000-12-04 2002-06-13 Univaton Technologies, Llc Procede de polymerisation
WO2002050088A1 (fr) 2000-12-18 2002-06-27 Univation Technologies, Llc Preparation de catalyseurs de polymerisation
US6562905B1 (en) 1998-04-06 2003-05-13 Borealis Technology Oy High density polyethylene compositions, a process for the production thereof and films prepared
US6627713B2 (en) 1994-08-02 2003-09-30 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization process
WO2004026921A1 (fr) 2002-09-20 2004-04-01 Exxonmobil Chemical Patents Inc. Production de polymeres dans des conditions supercritiques
US6884748B2 (en) 2002-09-04 2005-04-26 Univation Technologies, Llc Process for producing fluorinated catalysts
US6958306B2 (en) 2003-08-28 2005-10-25 Univation Technologies, Llc Activated catalyst systems from substituted dialuminoxane complexes
WO2005113615A2 (fr) 2004-05-20 2005-12-01 Univation Technologies, Llc Procede de polymerisation
US6995109B2 (en) 2001-11-30 2006-02-07 Univation Technologies, Llc Method of making a bimetallic catalyst with higher activity
WO2006019494A1 (fr) 2004-07-14 2006-02-23 Exxonmobil Chemical Patents Inc. Synthèse de polymères en conditions supercritiques
US7129302B2 (en) 2000-11-30 2006-10-31 Univation Technologies, Llc Bimetallic catalyst for producing polyethylene resins with bimodal molecular weight distribution, its preparation and use
US7157531B2 (en) 2004-06-21 2007-01-02 Univation Technologies, Llc Methods for producing polymers with control over composition distribution
US7169864B2 (en) 2004-12-01 2007-01-30 Novolen Technology Holdings, C.V. Metallocene catalysts, their synthesis and their use for the polymerization of olefins
US7179876B2 (en) 2001-07-19 2007-02-20 Univation Technologies, Llc High tear films from hafnocene catalyzed polyethylenes
US20070055028A1 (en) 2004-01-07 2007-03-08 Casty Gary L Preparation of polymerization catalyst activators utilizing indole-modified silica supports
US20070060721A1 (en) 2005-09-14 2007-03-15 Muhle Michael E Method for operating a gas-phase reactor at or near maximum production rates while controlling polymer stickiness
EP1806368A2 (fr) 2000-10-13 2007-07-11 Univation Technologies LLC Procédé de polymérisation en présence d'un système catalytique sur support
US20080065360A1 (en) 2006-09-07 2008-03-13 Univation Technologies, Llc Methods for on-line determination of degree of resin stickiness using a model for depression of melt initiation temperature

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2618384B2 (ja) * 1986-12-27 1997-06-11 三井石油化学工業株式会社 オレフイン重合用固体触媒およびその製法
ES2160182T3 (es) * 1994-12-15 2001-11-01 Exxonmobil Chem Patents Inc Sistemas catalizadores de polimerizacion, su produccion y uso.
CA2167983C (fr) * 1995-01-25 2001-01-09 Toshiyuki Tsutsui Catalyseur deshydrate prepolymerise pour la polymerisation d'olefines; methode de preparation de ce catalyseur; procede de polymerisation d'olefines en phase gazeuse
FI974175A (fi) * 1997-11-07 1999-05-08 Borealis As Menetelmä polypropeenin valmistamiseksi
US6245868B1 (en) * 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
US6894131B2 (en) * 1998-08-21 2005-05-17 Univation Technologies, Llc Polymerization process using a metallocene catalyst system
US6914027B2 (en) 2000-12-01 2005-07-05 Univation Technologies, Llc Polymerization reactor operability using static charge modifier agents
US7799877B2 (en) * 2001-11-15 2010-09-21 Univation Technologies, Llc Polymerization monitoring and control using leading indicators
CN100513429C (zh) * 2004-01-02 2009-07-15 尤尼威蒂恩技术有限责任公司 控制气相反应器中的结皮的方法
US7985811B2 (en) * 2004-01-02 2011-07-26 Univation Technologies, Llc Method for controlling sheeting in gas phase reactors
CN101627060B (zh) * 2006-07-31 2011-11-30 尤尼威蒂恩技术有限公司 用于控制聚烯烃反应器中的静电荷的方法和装置
ES2401040T3 (es) * 2007-08-16 2013-04-16 Univation Technologies, Llc Aditivos de continuidad y su uso en procesos de polimerización

Patent Citations (116)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324095A (en) 1965-05-14 1967-06-06 Union Carbide Corp Polymerization process
US4003712A (en) 1970-07-29 1977-01-18 Union Carbide Corporation Fluidized bed reactor
US3709853A (en) 1971-04-29 1973-01-09 Union Carbide Corp Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts
BE839380A (fr) 1975-03-10 1976-09-10 Procede de preparation de copolymeres d'ethylene de faible densite
US4011382A (en) 1975-03-10 1977-03-08 Union Carbide Corporation Preparation of low and medium density ethylene polymer in fluid bed reactor
US4302565A (en) 1978-03-31 1981-11-24 Union Carbide Corporation Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization
US4302566A (en) 1978-03-31 1981-11-24 Union Carbide Corporation Preparation of ethylene copolymers in fluid bed reactor
US4621952A (en) 1981-07-28 1986-11-11 Union Carbide Corporation Fluidized bed discharge process
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
EP0102503A2 (fr) 1982-07-26 1984-03-14 Toyo Stauffer Chemical Co. Ltd. Procédé de préparation d'un composant de catalyseur utilisé pour la polymérisation des alpha-oléfines
EP0103120A2 (fr) 1982-07-26 1984-03-21 Toyo Stauffer Chemical Co. Ltd. Procédé de préparation d'un composant de catalyseur utilisé pour la polymérisation des alpha-oléfines
US4935474A (en) 1983-06-06 1990-06-19 Exxon Research & Engineering Company Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4937299A (en) 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US4877587A (en) 1984-08-24 1989-10-31 Union Carbide Chemicals And Plastics Company Inc. Fluidized bed polymerization reactors
US4933149A (en) 1984-08-24 1990-06-12 Union Carbide Chemicals And Plastics Company Inc. Fluidized bed polymerization reactors
US4665208A (en) 1985-07-11 1987-05-12 Exxon Chemical Patents Inc. Process for the preparation of alumoxanes
US5124418A (en) 1985-11-15 1992-06-23 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4701432A (en) 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
USRE33683E (en) 1986-01-24 1991-09-03 Mobil Oil Corporation Catalyst composition for polymerizing alpha-olefins
EP0231102A2 (fr) 1986-01-24 1987-08-05 Mobil Oil Corporation Composition de catalyseur pour polymérisation d'oléfines
US5183867A (en) 1986-09-09 1993-02-02 Exxon Chemical Patents Inc. Polymerization process using a new supported polymerization catalyst
US5077255A (en) 1986-09-09 1991-12-31 Exxon Chemical Patents Inc. New supported polymerization catalyst
EP0594218A1 (fr) 1986-09-24 1994-04-27 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfines
US5204419A (en) 1986-11-20 1993-04-20 Mitsui Petrochemical Industries, Ltd. Process for polymerizing olefins
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5278119A (en) 1987-01-30 1994-01-11 Exxon Chemical Patents Inc. Catalysts, method of preparing these catalysts, and polymerization processes wherein these catalysts are used
US5241025A (en) 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
EP0277004A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs et procédé d'utilisation
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
EP0277003A1 (fr) 1987-01-30 1988-08-03 Exxon Chemical Patents Inc. Catalyseurs, méthode de préparation de ces catalyseurs, et procédé de polymérisation en utilisant ces catalyseurs
US4952540A (en) 1987-02-14 1990-08-28 Mitsui Petrochemical Industries, Ltd. Finely divided aluminoxane, process for producing same and its use
EP0279586B1 (fr) 1987-02-14 1994-05-04 Mitsui Petrochemical Industries, Ltd. Aluminoxane finement divisé, son procédé de fabrication et son utilisation
US4874734A (en) 1987-04-03 1989-10-17 Mitsui Petrochemical Industries, Ltd. Process for producing solid catalyst for polymerization of olefins
US5206199A (en) 1987-04-20 1993-04-27 Mitsui Petrochemical Industries, Ltd. Catalyst for polymerizing an olefin and process for polymerizing an olefin
US5093415A (en) 1987-05-19 1992-03-03 Union Carbide Chemicals & Plastics Technology Corporation Process for producing stereoregular polymers having a narrow molecular weight distribution
US4882400A (en) 1987-07-31 1989-11-21 Bp Chemicals Limited Process for gas phase polymerization of olefins in a fluidized bed reactor
US5028670A (en) 1988-07-15 1991-07-02 Bp Chemicals Limited Process for the gas-phase polymerization of olefins in a fluidized-bed reactor
US5091352A (en) 1988-09-14 1992-02-25 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst component, olefin polymerization catalyst and process for the polymerization of olefins
WO1990003414A1 (fr) 1988-09-30 1990-04-05 Exxon Chemical Patents Inc. Melanges lineaires d'interpolymeres ethyleniques a distribution etroite de leur poids moleculaire et de leur composition
US4908463A (en) 1988-12-05 1990-03-13 Ethyl Corporation Aluminoxane process
US5103031A (en) 1989-02-21 1992-04-07 Ethyl Corporation Falling film aluminoxane process
US4968827A (en) 1989-06-06 1990-11-06 Ethyl Corporation Alkylaluminoxane process
US4924018A (en) 1989-06-26 1990-05-08 Ethyl Corporation Alkylaluminoxane process
US5387568A (en) 1989-10-30 1995-02-07 Fina Technology, Inc. Preparation of metallocene catalysts for polymerization of olefins
EP0426637A2 (fr) 1989-10-30 1991-05-08 Fina Technology, Inc. Préparation de catalyseurs métallocènes pour la polymérisation d'oléfines
US5066741A (en) 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
EP0500944A1 (fr) 1990-07-24 1992-09-02 MITSUI TOATSU CHEMICALS, Inc. CATALYSEUR POUR POLYMERISATION $g(a)-OLEFINIQUE ET PRODUCTION D'UNE POLY-$g(a)-OLEFINE A L'AIDE DE CE CATALYSEUR
EP0495375A2 (fr) 1991-01-16 1992-07-22 The Dow Chemical Company Procédé de préparation de catalyseurs pour polymérisation par addition par oxydation de centres métalliques
US5206197A (en) 1991-03-04 1993-04-27 The Dow Chemical Company Catalyst composition for preparation of syndiotactic vinyl aromatic polymers
EP0520732A1 (fr) 1991-06-24 1992-12-30 The Dow Chemical Company Catalyseur homogène de polymérisation d'olefines obtenu par élimination d'un ligand avec un acide de lewis
US5157137A (en) 1991-07-26 1992-10-20 Ethyl Corporation Method of making gel free alkylaluminoxane solutions
US5308815A (en) 1991-07-26 1994-05-03 Ethyl Corporation Heterogeneous methylaluminoxane catalyst system
US5395810A (en) 1991-09-30 1995-03-07 Fina Technology, Inc. Method of making a homogeneous-heterogenous catalyst system for olefin polymerization
US5281679A (en) 1991-11-07 1994-01-25 Exxon Chemical Patents Inc. Catalyst and method of broadening polymer molecular weight distribution and increasing polymer tensile impact strength and products made thereof
US5391660A (en) 1992-01-14 1995-02-21 Nippon Oil Company, Limited Process for preparing polyolefines
EP0561476A1 (fr) 1992-03-18 1993-09-22 Akzo Nobel N.V. Solution de polyméthylaluminoxane avec stabilisation améliorée de la solution
US5235081A (en) 1992-03-18 1993-08-10 Ethyl Corporation Method of removing gel forming materials from methylaluminoxanes
US5329032A (en) 1992-03-18 1994-07-12 Akzo Chemicals Inc. Polymethylaluminoxane of enhanced solution stability
US5352749A (en) 1992-03-19 1994-10-04 Exxon Chemical Patents, Inc. Process for polymerizing monomers in fluidized beds
US5436304A (en) 1992-03-19 1995-07-25 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5288933A (en) 1992-04-16 1994-02-22 Union Carbide Chemicals & Plastics Technology Corporation Process for the production of polyethylene
EP0570982A1 (fr) 1992-05-22 1993-11-24 Tosoh Corporation Catalyseurs et procédé de préparation de polymères d'oléfine
US5290745A (en) 1992-08-10 1994-03-01 Union Carbide Chemicals & Plastics Technology Corporation Process for producing ethylene polymers having reduced hexane extractable content
US5248801A (en) 1992-08-27 1993-09-28 Ethyl Corporation Preparation of methylaluminoxanes
WO1994007928A1 (fr) 1992-10-02 1994-04-14 The Dow Chemical Company Complexes de catalyseurs supportes et homogenes utilises dans la polymerisation d'olefines
US5317036A (en) 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
US5391793A (en) 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes
WO1994010180A1 (fr) 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5391529A (en) 1993-02-01 1995-02-21 Albemarle Corporation Siloxy-aluminoxane compositions, and catalysts which include such compositions with a metallocene
US5405922A (en) 1993-04-26 1995-04-11 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5462999A (en) 1993-04-26 1995-10-31 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5668228A (en) 1993-05-20 1997-09-16 Bp Chemicals Limited Polymerization process
EP0802202B1 (fr) 1993-05-20 1999-10-27 BP Chemicals Limited Réacteur de polymérisation à lit fluidisé
EP0802202A1 (fr) 1993-05-20 1997-10-22 BP Chemicals Limited Réacteur de polymérisation à lit fluidisé
US5541270A (en) 1993-05-20 1996-07-30 Bp Chemicals Limited Polymerization process
EP0703246A1 (fr) 1993-07-13 1996-03-27 BP Chemicals Limited Procédé de polymérisation d'oléfine avec un catalyseur Ziegler-Natta
EP0634421B1 (fr) 1993-07-13 1997-10-08 Mitsui Petrochemical Industries, Ltd. Procédé de polymérisation d'oléfine en phase gazeuse
US5518973A (en) 1993-10-15 1996-05-21 Exxon Chemical Patents Inc. Titanium trichloride catalyst system for polymerizing olefins
US5466649A (en) 1993-10-15 1995-11-14 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
EP0649992B1 (fr) 1993-10-23 1997-07-30 WABCO GmbH Moteur de frein à disque
US6627713B2 (en) 1994-08-02 2003-09-30 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization process
US5453471A (en) 1994-08-02 1995-09-26 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization process
US5453471B1 (en) 1994-08-02 1999-02-09 Carbide Chemicals & Plastics T Gas phase polymerization process
US5525678A (en) 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
US5616661A (en) 1995-03-31 1997-04-01 Union Carbide Chemicals & Plastics Technology Corporation Process for controlling particle growth during production of sticky polymers
US5677375A (en) 1995-07-21 1997-10-14 Union Carbide Chemicals & Plastics Technology Corporation Process for producing an in situ polyethylene blend
WO1997022635A1 (fr) 1995-12-19 1997-06-26 Exxon Chemical Patents Inc. Procede de polymerisation d'olefine a haute temperature
EP0794200A2 (fr) 1996-03-05 1997-09-10 Union Carbide Chemicals & Plastics Technology Corporation Procédé de polymérisation dans une séquence de réacteurs
US5665818A (en) 1996-03-05 1997-09-09 Union Carbide Chemicals & Plastics Technology Corporation High activity staged reactor process
US5627242A (en) 1996-03-28 1997-05-06 Union Carbide Chemicals & Plastics Technology Corporation Process for controlling gas phase fluidized bed polymerization reactor
US6255426B1 (en) 1997-04-01 2001-07-03 Exxon Chemical Patents, Inc. Easy processing linear low density polyethylene
US6069213A (en) 1997-12-16 2000-05-30 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst system
US6562905B1 (en) 1998-04-06 2003-05-13 Borealis Technology Oy High density polyethylene compositions, a process for the production thereof and films prepared
WO2000069922A2 (fr) 1999-05-17 2000-11-23 Univation Technologies, Llc Procede de polymerisation
WO2001030860A1 (fr) 1999-10-22 2001-05-03 Univation Technologies, Llc Systemes catalyseurs et leur utilisation dans un procede de polymerisation
WO2001030861A1 (fr) 1999-10-22 2001-05-03 Univation Technologies, Llc Compositions catalytiques, procedes de polymerisation et polymeres fabriques a partir de ces compositions
EP1806368A2 (fr) 2000-10-13 2007-07-11 Univation Technologies LLC Procédé de polymérisation en présence d'un système catalytique sur support
US7129302B2 (en) 2000-11-30 2006-10-31 Univation Technologies, Llc Bimetallic catalyst for producing polyethylene resins with bimodal molecular weight distribution, its preparation and use
WO2002046246A2 (fr) 2000-12-04 2002-06-13 Univaton Technologies, Llc Procede de polymerisation
US6689847B2 (en) 2000-12-04 2004-02-10 Univation Technologies, Llc Polymerization process
WO2002050088A1 (fr) 2000-12-18 2002-06-27 Univation Technologies, Llc Preparation de catalyseurs de polymerisation
US7179876B2 (en) 2001-07-19 2007-02-20 Univation Technologies, Llc High tear films from hafnocene catalyzed polyethylenes
US6995109B2 (en) 2001-11-30 2006-02-07 Univation Technologies, Llc Method of making a bimetallic catalyst with higher activity
US6884748B2 (en) 2002-09-04 2005-04-26 Univation Technologies, Llc Process for producing fluorinated catalysts
WO2004026921A1 (fr) 2002-09-20 2004-04-01 Exxonmobil Chemical Patents Inc. Production de polymeres dans des conditions supercritiques
US6958306B2 (en) 2003-08-28 2005-10-25 Univation Technologies, Llc Activated catalyst systems from substituted dialuminoxane complexes
US20070055028A1 (en) 2004-01-07 2007-03-08 Casty Gary L Preparation of polymerization catalyst activators utilizing indole-modified silica supports
WO2005113615A2 (fr) 2004-05-20 2005-12-01 Univation Technologies, Llc Procede de polymerisation
US7122607B2 (en) 2004-05-20 2006-10-17 Univation Technologies, Llc Polymerization process
US7157531B2 (en) 2004-06-21 2007-01-02 Univation Technologies, Llc Methods for producing polymers with control over composition distribution
WO2006019494A1 (fr) 2004-07-14 2006-02-23 Exxonmobil Chemical Patents Inc. Synthèse de polymères en conditions supercritiques
US7169864B2 (en) 2004-12-01 2007-01-30 Novolen Technology Holdings, C.V. Metallocene catalysts, their synthesis and their use for the polymerization of olefins
US20070060721A1 (en) 2005-09-14 2007-03-15 Muhle Michael E Method for operating a gas-phase reactor at or near maximum production rates while controlling polymer stickiness
US20080065360A1 (en) 2006-09-07 2008-03-13 Univation Technologies, Llc Methods for on-line determination of degree of resin stickiness using a model for depression of melt initiation temperature

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"HAWLEY'S CONDENSED CHEMICAL DICTIONARY", 1997, JOHN WILEY & SONS, INC., article "NEW NOTATION"
"METALLOCENE-BASED POLYOLEFINS", 2000, JOHN WILEY & SONS, LTD.
G. G. HLATKY, 181 COORDINATION CHEM. REV., 1999, pages 243 - 296
METALLOCENE-BASED POLYOLEFINS, 2000, pages 261 - 377

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2632878C2 (ru) * 2011-12-31 2017-10-11 Юнивейшн Текнолоджиз, Ллк Добавка для повышения сплошности для процессов полимеризации олефинов
WO2022109518A1 (fr) * 2020-11-17 2022-05-27 Exxonmobil Chemical Patents Inc. Procédé de démarrage d'un réacteur en phase gazeuse
CN117567676A (zh) * 2024-01-16 2024-02-20 新疆独山子石油化工有限公司 一种钛系聚乙烯转产茂金属聚乙烯的生产方法
CN117567676B (zh) * 2024-01-16 2024-04-16 新疆独山子石油化工有限公司 一种钛系聚乙烯转产茂金属聚乙烯的生产方法

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