WO2000037511A2 - Systeme catalytique de polymerisation d'olefine, procede de polymerisation et polymere ainsi obtenu - Google Patents

Systeme catalytique de polymerisation d'olefine, procede de polymerisation et polymere ainsi obtenu Download PDF

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Publication number
WO2000037511A2
WO2000037511A2 PCT/US1999/027502 US9927502W WO0037511A2 WO 2000037511 A2 WO2000037511 A2 WO 2000037511A2 US 9927502 W US9927502 W US 9927502W WO 0037511 A2 WO0037511 A2 WO 0037511A2
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WIPO (PCT)
Prior art keywords
group
catalyst
composition
methyl
polyolefin
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PCT/US1999/027502
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English (en)
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WO2000037511A3 (fr
Inventor
Rex E. Murray
Simon Mawson
Clark C. Williams
David James Schreck
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Univation Technologies, Llc
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Priority claimed from US09/213,627 external-priority patent/US6320002B1/en
Priority claimed from US09/216,215 external-priority patent/US6303719B1/en
Priority claimed from US09/215,706 external-priority patent/US6268447B1/en
Priority to JP2000589580A priority Critical patent/JP2002533483A/ja
Priority to BR9916313-6A priority patent/BR9916313A/pt
Priority to PL99348825A priority patent/PL348825A1/xx
Application filed by Univation Technologies, Llc filed Critical Univation Technologies, Llc
Priority to CA002350451A priority patent/CA2350451A1/fr
Priority to MXPA01006185A priority patent/MXPA01006185A/es
Priority to EP99963936A priority patent/EP1144465A2/fr
Priority to AU20272/00A priority patent/AU756833B2/en
Publication of WO2000037511A2 publication Critical patent/WO2000037511A2/fr
Publication of WO2000037511A3 publication Critical patent/WO2000037511A3/fr
Priority to NO20012982A priority patent/NO20012982L/no

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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • This invention relates to olefm polymerization catalyst systems comprising activators and catalysts based upon transition metal compounds comprising bidentate ligands containing pyridine or quinoline moieties and mixtures thereof, polymerization processes using such catalyst systems and polymer produced therefrom.
  • non-metallocene, homogeneous catalysts The intense commercialization of metallocene polyolefin catalysts has led to widespread interest in the design of non-metallocene, homogeneous catalysts. This field is more than an academic curiosity as new, non-metallocene catalysts may provide an easier pathway to currently available products and may also provide product and process opportunities which are beyond the capability of metallocene catalysts. In addition, certain non-cyclopentadienyl ligands may be more economical due to the relative ease of synthesis of a variety of substituted analogs.
  • This invention relates to an olefin polymerization catalyst system comprising at least one activator and one of: a) at least two transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, as described below as represented by formula I, II, III or IV, b) the product of the combination of an activator and a transition metal catalyst based on bidentate ligands containing pyridine or quinoline moieties, such as those described as represented by formula III or IV, that has been allowed to react prior to the introduction into the reactor, preferably for at least 15 minutes, and/or c) the product of combination of an additive and a transition metal catalyst based on bidentate ligands containing pyridine or quinoline moieties, such as those described below as represented by formula I or II.
  • This invention further relates to a polymer produced therefrom, particularly to a unique polyethylene resins, more preferably bimodal high density polyethylene resins produced by this invention.
  • Figures 1-5 are plots of the log of weight average molecular weight versus the dwt/d(logM), a measure of molecular weight distribution for the runs in Table 1.
  • Figures 6 and 7 are the size exclusion chromatography (SEC) graphs for the runs in examples 11 and 12.
  • Figure 8 is the SEC graph of the polymer produced in Example 14.
  • Figure 9 is the SEC Graph from Example 14 of USSN 09/103,620, filed June 23,
  • This invention relates in part to olefm polymerization catalyst system comprising at least one activator and at least two transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties.
  • the activator may be any known catalyst activator and in one embodiment is an alkyl aluminum, an alumoxane, a modified alumoxane, a polyalumoxane, a non-coordinating anion, a Lewis acid, a borane or a mixture thereof.
  • Ionizing compounds may contain an active proton, or some other cation associated with but not coordinated to or only loosely coordinated to the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197,
  • activators include those described in PCT publication WO 98/07515 such as tris (2, 2', 2"- nonafluorobiphenyl) fluoroaluminate, which is fully incorporated herein by reference.
  • Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, PCT publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410 all of which are herein fully incorporated by reference.
  • methods of activation such as using radiation and the like are also contemplated as activators for the purposes of this invention.
  • the activator is selected firm the following: tris(2,2',2"- nonafluorobiphenyl)fluoroaluminate, alumoxane, triphenyl boron, triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl borane, tri(n-butyl)ammonium tetrakis(pentafiuorophenyl)boron or a trisperfluorophenyl boron, or diehtylaluminum chloride.
  • transition metal catalyst compound based on bidentate ligands containing pyridine or quinoline moieties is represented by the formula:
  • M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, divalent or trivalent anion; X and Y are bonded to M; X and Y are independently carbon or a heteroatom, provided that at least one of X and Y is a heteroatom, preferably both X and Y are heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms or a silyl group, an alkyl silyl group such as a trialkyl silyl, preferably Z is a cyclic group containing 3 to
  • n is the oxidation state of M minus q minus 1 if Q is a monovalent anion, n is (the oxidation state of M -q)/2, if Q is a bivalent anion or n is (the oxidation state of M - q )/3 if Q is a trivalent anion., typically n is an integer from 1 to 4 depending on the oxidation state of M.
  • Z is optional. In another embodiment, if X is nitrogen or phosphorous then Z is present. In an embodiment, Z is preferably an aryl group, more preferably a substituted aryl group. In a preferred embodiment T is oxygen and is bound to an alkyl, aryl or alkaryl group.
  • transition metal catalyst compounds are represented by the formula:
  • M is a metal selected from Group 3 to 13 of the Periodic Table of Elements, preferably a Group 4 to 12 transition metal, more preferably a Group 4, 5 or 6 transition metal, even more preferably a Group 4 transition metal such as titanium, zirconium or hafnium, and most preferably zirconium;
  • each Q is bonded to M and each Q is a monovalent, divalent or trivalent anion.
  • each Q is independently selected from the group consisting of halogens, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarboxy or phenoxy radicals having 1-20 carbon atoms.
  • Each Q may also be amides, phosphides, sulfides, silylalkyls, diketonates, and carboxylates.
  • each Q may contain one or more heteroatoms, more preferably each Q is selected from the group consisting of halides, alkyl radicals and arylalkyl radicals.
  • each Q is selected from the group consisting of arylalkyl radicals such as benzyl.
  • X and Y are both bound to M and are independently carbon or a heteroatom, provided that at least one of X and Y is a heteroatom, X and Y are preferably each heteroatoms, more preferably X and Y are independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorous, even more preferably nitrogen or phosphorous, and most preferably nitrogen;
  • Y is contained in a heterocyclic ring or ring system J.
  • J contains from 2 to 30 carbon atoms, preferably from 2 to 7 carbon atoms, more preferably from 3 to 6 carbon atoms, and most preferably 5 carbon atoms.
  • the heterocyclic ring J containing Y may contain additional heteroatoms.
  • J may be substituted with R" groups that are independently selected from the group consisting of hydrogen or linear, branched, cyclic, alkyl radicals, or alkenyl, alkynyl, alkoxy, aryl or aryloxy radicals.
  • two or more R" groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring.
  • R" is hydrogen or an aryl group, most preferably R" is hydrogen.
  • R" is an aryl group and Y is nitrogen, a quinoline group is formed.
  • an R" may be joined to A;
  • Z is a hydrocarbyl group bonded to X, preferably Z is a hydrocarbyl group of from
  • Z is a cyclic group having from 3 to 30 carbon atoms, preferably Z is a substituted or unsubstituted cyclic group containing from 3 to 30 carbon atoms, optionally including one or more heteroatoms, more preferably Z is an aryl group, most preferably a substituted aryl group in another embodiment Z may be silyl or an alkyl silyl, preferably a trialkyl silyl;
  • Z may be substituted with R' groups that are independently selected from group consisting of hydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl, alkynyl or aryl radicals. Also, two or more R' groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring.
  • R' is an alkyl group having from 1 to 20 carbon atoms, more preferably R' is methyl, ethyl, propyl, butyl, pentyl and the like, including isomers thereof, more preferably R' is a methyl group, or a primary, secondary or tertiary hydrocarbon, including isopropyl, t-butyl and the like, most preferably R' is an isopropyl group.
  • an R' group may be joined to A. It is preferred that at least one R' is ortho to X;
  • Bridging group A is a bridging group joined to at least one of, preferably both of, X and J.
  • Bridging group A contains one or more Group 13 to 16 elements from Periodic Table of Elements. More preferably A contains one or more Group 14 elements, most preferably A is a substituted carbon group, a di-substituted carbon group or vinyl group; and
  • n and p are independently an integer from 0 to 5, preferably m is 2; n is the oxidation state of M minus q minus 1 if Q is a monovalent anion, n is (the oxidation state of M -q)/2, if Q is a bivalent anion or n is (the oxidation state of M - q)/3 if Q is a trivalent anion, preferably n is an integer from 1 to 4; and q is 1 or 2, and where q is 2, the two ((R' m Z)XA(YJR" m )) of formula (II) are bridged to each other via a bridging group, preferably a bridging group containing a Group 14 element.
  • the second catalyst is the same as the first catalyst except that one Q group is a hydrocarboxy group, a boronate or an amide.
  • the second catalyst is the same as the first catalyst except that one Q group is an alkoxide, phenoxide, acetylacetonate, carboxylate, cyclopentadienyl, flourenyls or an indenyl group.
  • the second catalyst is the same as the first catalyst except that one Q group of the second catalyst is a hydrocarboxy adduct of the analogous Q group on the first catalyst, preferably an alkoxide adduct, a boronate, a phenoxide adduct, an acetylacetonate adduct, a carboxylate adduct, an amide adduct, a cyclopentadienyl adduct, a flourenyl adduct or an indenyl adduct.
  • one Q group of the second catalyst is a hydrocarboxy adduct of the analogous Q group on the first catalyst, preferably an alkoxide adduct, a boronate, a phenoxide adduct, an acetylacetonate adduct, a carboxylate adduct, an amide adduct, a cyclopentadienyl adduct, a floureny
  • At least one of the transition metal catalyst compounds is represented by the formula:
  • M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; T is bonded to M and is an element from Group 13 to 16, preferably oxygen, boron, nitrogen, silicon, phosphorus, sulfur or aluminum and T may also be bound to one or more Cl to C50 groups optionally containing one or more heteroatoms, preferably T is a hydrocarboxy group, a boronate group or an amide group, preferably an alkoxide, phenoxide, acetylacetonate, or carboxylate or a cyclopentadienide group such as cyclopentadienyls, flourenyls and indenyls, Q is bonded to M and each Q is a monovalent, divalent or trivalent anion; X and Y are bonded to M; X and Y are independently C or a heteroatom, provided that at least one of X and Y is a heteroatom, preferably both X and Y are heteroatom
  • At least one of the transition metal catalyst compounds is represented by the formula:
  • M is a metal selected from Group 3 to 13 of the Periodic Table of Elements, preferably a Group 4 to 12 transition metal, more preferably a Group 4, 5 or 6 transition metal, even more preferably a Group 4 transition metal such as titanium, zirconium or hafnium, and most preferably zirconium;
  • T is bonded to M and is an element from Group 13 to 16, preferably oxygen, boron, nitrogen, silicon, phosphorus, sulfur or aluminum and T may also be bound to one or more Cl to C50 groups optionally containing one or more heteroatoms, T is preferably a hydrocarboxy group, a boronate, or an amide, preferably an alkoxide, phenoxide, acetylacetonate, or carboxylate or a cyclopentadienide group such as cyclopentadienyls, flourenyls and indenyls.
  • each Q is bonded to M and each Q is a monovalent, divalent or trivalent anion.
  • each Q is independently selected from the group consisting of halogens, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarboxy or phenoxy radicals having 1-20 carbon atoms.
  • Each Q may also be amides, phosphides, sulfides, silylalkyls, diketonates, and carboxylates.
  • each Q may contain one or more heteroatoms, more preferably each Q is selected from the group consisting of halides, alkyl radicals and arylalkyl radicals.
  • each Q is selected from the group consisting of arylalkyl radicals such as benzyl.
  • X and Y are independently C or a heteroatom, provided that at least one of X and
  • Y is a heteroatom
  • X and Y are preferably each heteroatoms, more preferably independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorous, even more preferably nitrogen or phosphorous, and most preferably nitrogen;
  • Y is contained in a heterocyclic ring or ring system J.
  • J contains from 2 to 30 carbon atoms, preferably from 2 to 7 carbon atoms, more preferably from 3 to 6 carbon atoms, and most preferably 5 carbon atoms.
  • the heterocyclic ring J containing Y may contain additional heteroatoms. J may be substituted with
  • R" groups that are independently selected from the group consisting of hydrogen or linear, branched, cyclic, alkyl radicals, or alkenyl, alkynyl, alkoxy, aryl or aryloxy radicals. Also, two or more R" groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring.
  • R" is hydrogen or an aryl group, most preferably R" is hydrogen.
  • R" is an aryl group and Y is nitrogen, a quinoline group is formed.
  • an R" may be joined to A;
  • Z is a hydrocarbyl group bonded to X, preferably Z is a hydrocarbyl group of from 1 to 50 carbon atoms, preferably Z is a cyclic group having from 3 to 30 carbon atoms, preferably Z is a substituted or unsubstituted cyclic group containing from 3 to 30 carbon atoms, optionally including one or more heteroatoms, Z may be a silyl group, an alkylsilyl group or a trialkyl, in another embodiment Z is not an aryl group;
  • Z may be substituted with R' groups that are independently selected from group consisting of hydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl, or alkynyl radicals. Also, two or more R' groups may be joined to form a cyclic moiety such as an aliphatic or aromatic ring.
  • R' is an alkyl group having from 1 to 20 carbon atoms, more preferably R' is methyl, ethyl, propyl, butyl, pentyl and the like, including isomers thereof, more preferably R' is a methyl group or a primary, secondary or tertiary hydrocarbon, including isopropyl, t-butyl and the like, most preferably R' is an isopropyl group.
  • an R' group may be joined to A. It is preferred that at least one R' is ortho to X;
  • Bridging group A is a bridging group joined to at least one of, preferably both of, X and J.
  • Bridging group A contains one or more Group 13 to 16 elements from Periodic
  • A contains one or more Group 14 elements, most preferably A is a substituted carbon group, a di-substituted carbon group or vinyl group;
  • n and p are independently an integer from 0 to 5, preferably m is
  • n is the oxidation state of M minus q minus s if Q is a monovalent anion, n is (the oxidation state of M -q-s)/2, if Q is a bivalent anion or n is (the oxidation state of M - q - s)/3 if Q is a trivalent anion, and where q is 2, the two ((R' m Z)XA(YJR" m )) of formula (IV) are bridged to each other via a bridging group, preferably a bridging group containing a Group 14 element.
  • J is pyridine in any of the above formulae.
  • the transition metal compounds may be made by any method known in the art.
  • the transition metal compound is [[l-(2-Pyridal)N-l-
  • [[l-(2-Pyridal)N-l- Methylethyl]-[ 1 -N-2,6-Diisopropylphenyl Amido]] [2-Methyl- 1 -Phenyl-2-Propoxy] Zirconium Dibenzyl is used in combination with an alumoxane, preferably methylalumoxane, more preferably a modified methyl alumoxane in a gas or slurry phase reactor to produce polyethylene, preferably high density polyethylene.
  • a non-coordination anion such as tri(n- butyl)ammonium tetrakis (pentafluorophenyl)boron or trisperfluorophenyl boron, is used in combination with the [[l-(2-Pyridal)N-l-Methylethyl]-[l-N-2,6- Diisopropylphenyl Amido]] [2-Methyl- 1 -Phenyl-2-Propoxy] Zirconium Dibenzyl in a gas or slurry phase reactor.
  • a non-coordination anion such as tri(n- butyl)ammonium tetrakis (pentafluorophenyl)boron or trisperfluorophenyl boron
  • activator is selected from the following: tris (2J'J"- nonafluorobiphenyl) fluoroaluminate, alumoxane, triphenyl boron, triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl borate, tri(n-butyl) ammonium tetrakis (pentafiuorophenyl) boron, or a trisperfluorophenyl boron, or diethylaluminum chloride.
  • two or more catalysts are selected to produce the desired product.
  • the two or more catalysts are selected from any of the above formulae.
  • two different catalyst form formula I may be selected, or a compound from formula I or II and a compound from formula III or IV can be combined.
  • two different catalysts falling within the definition of formula IV may be combined.
  • a compound from formula I or II is used together with at lease one compound from formulae III or IV. It is possible to obtain a bimodal product by selecting catalysts that are know to produce differing molecular weights.
  • the two catalysts are fed into the reactor separately.
  • a first catalyst as represented by formula I or II where at least one Q group is not an oxy-adduct is chosen and the second catalyst is the same as the first catalyst system except that one, two or all three of the Q groups is an oxy-adduct of the same Q group as is present in the first catalyst.
  • oxy-adduct is defined to be O- R where O is oxygen and R is a Ci to C 50 group which optionally may contain one or more heteroatoms.
  • Preferred R groups include t-butyl, t-amyl, t-hexyl, isopropyl, 2-[2-methyl-l-phenyl-propyl], 2-[2-benzyl-butyl], 3-[3-benzyl-pentyl].
  • R groups include benzyl, methyl benzyl, ethyl benzyl and the like.
  • the oxy adduct may be represented by the formula O-B-R, where O is oxygen, B is boron and R is a Ci to C 50 group which optionally may contain one or more heteroatoms.
  • R groups include t-butyl, t-amyl, t- hexyl, isopropyl, 2-[2-methyl-l-phenyl-propyl], 2-[2-benzyl-butyl], 3-[3-benzyl- pentyl].
  • Other possible R groups include, benzyl, methyl benzyl, ethyl benzyl and the like.
  • the two catalysts [l-(2-Pyridyl)N-l-Methylethyl][l-N- 2,6-Diisopropylphenyl Amido] Zirconium Tribenzyl and [[l-(2-Pyridyl)N-l- Methylethyl]-[ 1 -N-2,6-Diisopropylphenyl Amido]] [2-Methyl- 1 -Phenyl-2-Propoxy]
  • Zirconium Dibenzyl are used in combination with an alumoxane, preferably a methyl alumoxane, more preferably a modified methyl alumoxane in a gas phase or slurry reactor to produce polyethylene, preferably high density polyethylene or alternately low density polyethylene.
  • alumoxane preferably a methyl alumoxane, more preferably a modified methyl alumoxane in a gas phase or slurry reactor to produce polyethylene, preferably high density polyethylene or alternately low density polyethylene.
  • a non- coordinating anion such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenyl boron, is used in combination with the two catalysts, [ 1 -(2-Pyridyl)N- 1 -Methylethyl] [ 1 -N-2,6-Diisopropylphenyl Amido] Zirconium Tribenzyl and [[ 1 -(2-Pyridyl)N- 1 -Methylethyl]-[ 1 -N-2,6-Diisopropylphenyl Amido]] [2-Methyl- 1 -Phenyl-2-Propoxy] Zirconium Dibenzyl, in a gas phase or slurry phase reactor to produce polyolefin, preferably polyethylene.
  • a non- coordinating anion such as tri (n-butyl) ammonium tetra
  • the two catalyst compounds are typically combined in a ratio of from 0.001:1 to about 10,000:1, preferably 0.5:1 to 1,000:1.
  • the first catalyst is present at from about 0.5 to about 99.5 weight % and the second catalyst is preset at about 99.5 to about 0.5 weight %, based upon the weight of the two catalysts but not activators or supports, preferably 5 to 95 weight % first catalyst and 95 to 5 weight % for the second catalyst, preferably 10 to 90 weight % first catalyst and 90 to 10 weight % for the second catalyst.
  • the first catalyst is present at from about 0.5 to about 99.5 weight % and the second and third catalysts are preset at about 99.5 to about
  • This invention further relates to olefm polymerization catalyst systems comprising at least one activator and the product of the combination of an activator (as described above) and a transition metal catalyst represented by formula III or IV (as described above), that has been allowed to react prior to introduction into the reactor, preferably for at least 15 minutes.
  • a single transition metal compound represented by the formulae III or IV can be used to produce unique, preferably bimodal, polyolefms. It has been observed that temperature apparently affects the catalysts represented by formula III or IV and apparently produces additional species. While not wishing to be bound by any theory, it appears that this conversion provides the ability to produce bi-modal product.
  • transition metal compound and the activator are allowed to reactor for at least 15 minutes prior to being contacted with olefm, preferably at least 30 minutes, preferably at least 1 hour, preferably at least 4 hours.
  • the polymerization preferably occurs at a temperature of at least 80 °C, preferably at least 85°C, preferably at least 90°C, preferably at least 100 °C.
  • This invention further relates to an olefm polymerization catalyst system comprising at least one activator (as described above) and the product of combination of an additive and a transition metal catalyst based on bidentate ligands containing pyridine or quinoline moieties represented by formula I or II (as described above).
  • the additive is preferably an alkoxy compound.
  • the R group may also contain heteroatoms, in addition to the 1 to 100 carbon atoms.
  • Preferred alkoxy compounds include ketones and aldehydes.
  • alkoxy compounds include acetone, benzophenone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tertiary butyl ketone, acetophenone, cyclohexanone, cyclopentanone, benzaldehyde, pivaldehyde, ethyl n-propyl ketone, ethyl isopropyl ketone, and the like.
  • the additive is combined with the transition metal catalyst compound in an amount of 0.5 weight % to about 90 weight % based upon the weight of the transition metal catalyst compound and the additive, but not any activators or supports, preferably 1 weight % to about 80 weight %, more preferably 10 to 60 weight %.
  • the additive may be combined with the transition metal catalyst compound (with or without the activator) before being added to the polymerization reactor. In one embodiment the additive is added to the transition metal catalyst compound in line in the injection tube.
  • the activator is allowed to react with the transition metal catalyst compound (that has already been reacted with the additive) for at least 5 minutes before being combined with the olefm, preferably 10 minutes, more preferably 15 minutes. It has been noted that if the transition metal catalyst compound is simply combined with the additive then added directly to the reactor, that less bimodal product is obtained. If the additive and the transition metal compound are allowed to react then for a period of time then more bimodal product is obtained.
  • the additive and the transition metal catalyst compound are combined prior to being combined with the activator.
  • the transition metal catalyst, olefm and the activator are already present in the polymerization reactor and the additive is added.
  • the additive is to be added after the activator and the transition metal catalyst compound are already combined and the activator is alumoxane, then extra amounts of additive may be required.
  • additives may be used to achieve different effects on the polymer produced. For example using diethyl ketone as the additive produces a polymer having a higher molecular weight than does using methyl ethyl ketone as the additive. Likewise using methyl ethyl ketone as the additive produces a polymer having a higher molecular weight than using acetone as the additive does.
  • the transition metal catalyst compound, [l-(2- Pyridyl)N-l-Methylethyl][l-N-2, 6-Diisopropylphenyl Amido] Zirconium Tribenzyl and the additive acetone are used in combination with an alumoxane, preferably a methyl alumoxane, more preferably a modified methyl alumoxane in a gas phase or slurry reactor to produce polyethylene, preferably high density polyethylene.
  • a non-coordinating anion such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenyl boron, is used in combination with the transition metal catalyst compound, [l-(2- Pyridyl)N- 1 -Methyl ethyl] [ 1 -N-2,6-Diisopropylphenyl Amido] Zirconium Tribenzyl and acetone, in a gas phase or slurry phase reactor.
  • the transition metal catalyst compound [l-(2- Pyridyl)N- 1 -Methyl ethyl] [ 1 -N-2,6-Diisopropylphenyl Amido] Zirconium Tribenzyl and acetone
  • the additive may or may not be present when the activator is added to the transition 15 metal compound before or after being placed in the reactor.
  • two different transition metal compounds are used in combination with an activator and an additive in the same reactor.
  • the transition metal catalyst compound and activator are fed into the reactor separately from the additive. While not wishing to be bound by any theory, it appears that the additive reacts with the transition metal catalyst compound to provide another active catalyst species. In embodiments of the invention, it has been noted that temperature appears to affect the balance between the two forms of the catalyst. It seems that higher temperatures may drive the conversion of the transition metal catalyst compound in the presence of the additive to the second catalyst species. Thus by selecting the amount of additive and the temperature at which they are combined and/or used one can select for desired end products.
  • the catalyst component that produces the lower molecular weight is present at 10 ppm to 70 weight % based upon the weight of all the catalysts but not the activators or supports, preferably 100 ppm to 8 weight %, even more preferably 1000 ppm to 5 weight %.
  • the compound that produces the lower molecular weight is present at 30 to 70 weight % based upon the weight of all the catalysts but not the activators or supports, preferably 40 to 60 weight %, even more preferably 45 to 55 weight %.
  • the component that makes the low molecular weight portion is present is an amount that will produce 20-70 weight % of the final polymer product.
  • the two or more catalysts may be activated at the same or different times, before or after entry into the reactor, and before or after being placed on a support.
  • the multiple catalysts are activated by the same activator before being placed in the reactor.
  • one catalyst is activated before being placed in the reactor, and a second catalyst is added, optionally with no activator, the same activator or a different activator.
  • the catalysts are supported on the same support then activated with the same activator prior to being placed in the reactor.
  • the two catalysts are activated with the same or different activators then placed upon a support before being placed in the reactor.
  • one or more of the catalyst systems or components may be supported on an organic or inorganic support.
  • the support can be of any of the solid, porous supports.
  • Typical support materials include talc; inorganic oxides such as silica, magnesium chloride, alumina, silica-alumina; polymeric supports such as polyethylene, polypropylene, polystyrene; and the like.
  • Preferred supports include silica, clay, talc, magnesium chloride and the like.
  • the support is used in finely divided form. Prior to use the support is preferably partially or completely dehydrated. The dehydration may be done physically by calcining or by chemically converting all or part of the active hydroxyls.
  • US 4,808,561 which teaches how to support a metallocene catalyst system. The techniques used therein are generally applicable for this invention.
  • the catalysts may be placed on separate supports or may be placed on the same support. Likewise the activator may be placed on the same support as the catalyst or may be placed on a separate support.
  • the catalysts/catalyst systems and/or their components need not be feed into the reactor in the same manner. For example, one catalyst or its components may be slurried into the reactor on a support while the other catalyst or components may be provided in a solution.
  • the catalyst system is fed into the reactor in a solution or slurry.
  • Hydrocarbons are useful for the solutions or slurries.
  • the solution can be toluene, hexane, isopentane or a combination thereof such as toluene and isopentane or toluene and pentane.
  • a typical solution would be 0.02 to 0.05 mole catalyst in the hydrocarbon carrier, preferably isopentane or hexane.
  • the carrier for the catalyst system or its components is a super critical fluid, such as ethane or propane.
  • a super critical fluid such as ethane or propane.
  • the one or all of the catalysts are combined with up to 6 weight % of a metal stearate, (preferably a aluminum stearate, more preferably aluminum distearate) based upon the weight of the catalyst, any support and the stearate, preferably 2 to 3 weight %.
  • a solution of the metal stearate is fed into the reactor.
  • These agents may be dry tumbled with the catalyst or may be fed into the reactor in a solution with or without the catalyst system or its components.
  • the catalysts combined with the activators are tumbled with 1 weight % of aluminum distearate and/or 2 weight % of an antistat, such as a methoxylated amine, such as Witco's Kemamine AS- 990 from ICI Specialties in Bloomington Delaware.
  • an antistat such as a methoxylated amine, such as Witco's Kemamine AS- 990 from ICI Specialties in Bloomington Delaware.
  • the metal stearate and/or the anti-static agent may be slurried into the reactor in mineral oil, ground into a powder then suspended in mineral oil then fed into the reactor, or blown directly into the reactor as a powder.
  • the catalysts and catalyst systems described above are suitable for use in a solution, gas or slurry polymerization process or a combination thereof, most preferably a gas or slurry phase polymerization process.
  • this invention is directed toward the solution, slurry or gas phase polymerization reactions involving the polymerization of one or more of monomers having from 2 to 30 carbon atoms, preferably 2-12 carbon atoms, and more preferably 2 to 8 carbon atoms.
  • Preferred monomers include one or more of ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-l, hexene- 1, octene-1, decene-1, 3-methyl-pentene-l, and cyclic olefms or a combination thereof.
  • Other monomers can include vinyl monomers, diolefins such as dienes, polyenes, norbornene, norbornadiene, vinyl norbornene, ethylidene norbornene monomers.
  • a homopolymer of ethylene is produced.
  • a copolymer of ethylene and one or more of the monomers listed above is produced.
  • ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer.
  • the preferred comonomers are a combination of alpha-olefm monomers having 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, optionally with at least one diene monomer.
  • the preferred terpolymers include the combinations such as ethylene/butene-1/hexene- 1, ethylene/propylene/butene-1, propylene/ethylene/hexene-1, ethylene/propylene/ norbornene and the like.
  • the process of the invention relates to the polymerization of ethylene and at least one comonomer having from 4 to 8 carbon atoms, preferably 4 to 7 carbon atoms.
  • the comonomers are butene-1, 4-methyl-pentene-l J-methyl-pentene-1, hexene- 1 and octene-1, the most preferred being hexene- 1, butene-1 and octene-1.
  • a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization.
  • This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • the reactor pressure in a gas phase process may vary from about 10 psig (69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
  • the reactor temperature in the gas phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 1 15°C, more preferably in the range of from about 70°C to 110°C, and most preferably in the range of from about 70°C to about 95°C. In another embodiment when high density polyethylene is desired then the reactor temperature is typically between 70 and 105 °C.
  • the productivity of the catalyst or catalyst system in a gas phase system is influenced by the main monomer partial pressure.
  • the preferred mole percent of the main monomer, ethylene or propylene, preferably ethylene, is from about 25 to 90 mole percent and the comonomer partial pressure is in the range of from about
  • the reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over 100,000 lbs/hr ( 45,500 Kg/hr).
  • a slurry polymerization process generally uses pressures in the range of from about
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert.
  • a propane medium When used the process must be operated above the reaction diluent critical temperature and pressure.
  • a hexane or an isobutane medium is employed.
  • a preferred polymerization technique of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • a particle form polymerization or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • the preferred temperature in the particle form process is within the range of about 185°F (85°C) to about 230°F (110°C).
  • Two preferred polymerization methods for the slurry process are those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference.
  • the slurry process is carried out continuously in a loop reactor.
  • the catalyst as a slurry in isobutane or as a dry free flowing powder is injected regularly to the reactor loop, which is itself filled with circulating slurry of growing polymer particles in a diluent of isobutane containing monomer and comonomer.
  • Hydrogen optionally, may be added as a molecular weight control.
  • the reactor is maintained at a pressure of about 525 psig to 625 psig (3620 kPa to 4309 kPa) and at a temperature in the range of about 140 °F to about 220 °F (about 60 °C to about 104 °C) depending on the desired polymer density.
  • Reaction heat is removed through the loop wall since much of the reactor is in the form of a double- jacketed pipe.
  • the slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isobutane diluent and all unreacted monomer and comonomers.
  • the resulting hydrocarbon free powder is then compounded for use in various applications.
  • the reactor used in the slurry process of the invention is capable of and the process of the invention is producing greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr).
  • the slurry reactor used in the process of the invention is producing greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
  • the total reactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig (5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).
  • the concentration of ethylene in the reactor liquid medium is in the range of from about 1 to 10 weight percent, preferably from about 2 to about 7 weight percent, more preferably from about 2.5 to about 6 weight percent, most preferably from about 3 to about 6 weight percent.
  • Another process of the invention is where the process, preferably a slurry or gas phase process is operated in the absence of or essentially free of any scavengers, such as triethylaluminum, trirnethylaluminum, tri-isobutylaluminum and tri-n- hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
  • any scavengers such as triethylaluminum, trirnethylaluminum, tri-isobutylaluminum and tri-n- hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
  • the process is run with scavengers.
  • Typical scavengers include trimethyl aluminum, tri-isobutyl aluminum and an excess of alumoxane or modified alumoxane.
  • the proportions of the components of the feed catalyst solution can be varied to alter molecular weight and other properties. For example altering the catalyst ratios will alter flow index, melt index, melt flow ratio and/or density. For example, in a system where a catalyst represented by formula I and a catalyst represented by formula IV are combined, if the proportion of a catalyst represented by formula IV is increased then, more lower molecular weight material is produced thus increasing flow index, altering the molecular weight distribution.
  • the catalyst that produces the lower molecular weight component is present at a value to produce 45-65 weight % of the final polymer product.
  • Another method to alter the molecular weight is to add hydrogen to the system by increasing the hydrogen ethylene ratio.
  • a method to control the density is altering the comonomer content.
  • a method to control molecular weight distribution (Mw/Mn), flow index, and/or density comprising altering on line in a commercial scale gas phase reactor (i.e. having a volume of 1500 cubic feet (42.5 m 3 )or more) the reaction temp and/or the catalyst ratio in the intimately mixed catalyst solution and/or the hydrogen concentration and/or the activator to transition metal ratio, such as the aluminum/zirconium ratio is also provided herein.
  • a commercial scale gas phase reactor i.e. having a volume of 1500 cubic feet (42.5 m 3 )or more
  • the reaction temp and/or the catalyst ratio in the intimately mixed catalyst solution and/or the hydrogen concentration and/or the activator to transition metal ratio, such as the aluminum/zirconium ratio is also provided herein.
  • Injection and mixing temperatures also provide a means to alter product properties as temperature affects activation and/or solvent evaporation and thus alters the catalyst composition and hence alters the final product.
  • the sequence and timing of activation also provides an opportunity to alter the catalyst composition and thus the final product.
  • higher concentrations of methyl alumoxane in a system comprising (A). [l-(2-Pyridyl)N-l- Methylethyl][l-N-2,6-Diisopropylphenyl Amido] Zirconium Tribenzyl and (B).
  • reaction temperature we have noted that raising the reaction temperature increased the amount of the higher molecular weight component and unusually the two modes in the size exclusion chromatography graph moved closer together (that is the Mw/Mn became lower when compared to the same system at a lower temperature).
  • the ratio of the first catalyst to the second or additional catalyst is 5:95 to 95:5, preferably 25:75 to 75:25, even more preferably 40:60 to
  • the catalyst system in is liquid form and is introduced into the reactor into a resin particle lean zone.
  • a liquid catalyst system into a fluidized bed polymerization into a particle lean zone please see US 5,693,727, which is incorporated by reference herein.
  • An example of a typical polymerization is: Modified methylalumoxane in hydrocarbon such as hexane or isopentane (about 1 to 10 % aluminum) and 10-30 weight % of [l-(2-Pyridyl)N- 1 -Methylethyl] [l-N-2,6-Diisopropylphenyl Ainido] Zirconium Tribenzyl and 70-90 weight% of [[l-(2-Pyridyl)N-l-Methylethyl]-[l-N- 2,6-Diisopropylphenyl Amido]][2-Methyl-l-Phenyl-2-Propoxy] Zirconium Dibenzyl, are suspended in solution then dried, thereafter they are tumbled with 2 weight % aluminum distearate and then slurried into a fluidized bed gas phase reactor held at a temperature of about 85 to about 100°C in an Al to Zr ratio of about 500:
  • the polyolefin recovered typically has a melt index as measured by ASTM D-1238, Condition E, at 190°C of lg/lOmin or less.
  • the polyolefin is ethylene homopolymer or copolymer.
  • the comonomer is preferably a C3 to C20 linear branched or cyclic monomer, and in one embodiment is a C3 to C12 linear or branched alpha-olefin, preferably propylene, hexene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4- methyl-pentene-1, 3-methyl pentene-1, 3,5,5-trimethyl hexene 1, and the like.
  • the catalyst system described above is used to make a high density polyethylene having a density of between 0.925 and 0.965 g/cm (as measured by ASTM 2839), and/or a melt index of 1.0 or less g/lOmin or less (as measured by ASTM D-1238, Condition E, at 190°C).
  • the catalyst system described above is used to make a polyethylene of 0.85 to 0.924 g/cm 3 .
  • the polymer produced by this invention has a molecular weight distribution (Mw/Mn) of at least 10, preferably at least 15, preferably at least 20, even more preferably at least 30.
  • the polymers produced by this invention have the unique advantage of the two polymer products being so intimately blended that there is an even distribution of the two polymers across the polymer particles as they exit the reactor.
  • the unprocessed, untreated granular polymer is referred to as neat polymer.
  • the neat polymer is then separated into fractions by standard sieve sizes according to ASTM D 1921 particle size (sieve analysis) of plastic Materials, Method A or PEG Method 507.
  • Fraction 1, 4, 6 The individual fractions (Fraction 1, 4, 6) are then tested for physical properties. Melt index is measured according to ASTM 1238, condition E, 190°C.
  • Crystallinity is measured using X-ray diffraction as described in example 13 below.
  • melt indices of the different fractions do not vary significantly.
  • the melt indices of Fractions 1, 4 and 6 do not vary by more than 20% relative, preferably by not more than 15% relative, preferably by not more than 10% relative, preferably by not more than 8% relative, preferably by not more that 6% relative, preferably by not more than 4% relative.
  • Relative means relative to the mean of the values for Fractions 1 , 4 and 6.
  • Another unique attribute of the polymer produced herein is that the percent crystallinity of the different fractions do not vary significantly.
  • the percent crystallinity of Fractions 1, 4 arid 6 do not vary by more than 6 % relative, preferably by not more than 5% relative, preferably by not more than 4 % relative, preferably by not more than 3% relative, preferably by not more that 2 % relative.
  • Relative means relative to the mean of the values for Fractions 1, 4 and 6.
  • Mw/Mn of the different fractions do not vary significantly.
  • the Mw/Mn of Fractions 1,4, 5 and 6 do not vary by more than 20% relative, preferably by not more than 10% relative, preferably by not more than 8% relative, preferably by not more than 6% relative, preferably by not more that 4% relative, preferably by not more than 2% relative.
  • Mn and Mw were measured by gel permeation chromatography on a waters 150 °C GPC instrument equipped with differential refraction index detectors. The GPC columns were calibrated by running a series of narrow polystyrene standards and the molecular weights were calculated using broad polyethylene standards National Bureau of Standards 1496 for the polymer in question.
  • the polymer produced herein has an Mw/Mn of 8 or more, preferably 10 or more, preferably 12 or more.
  • a parameter of polymer produced is that the crystallite morphology varies with particle size.
  • Fraction 1 preferably has an aspect ratio of 0.5-1.5
  • fraction 4 has an aspect ratio of 1.2 to 4
  • Fraction 6 has an aspect ratio of about 1.75 to 5 provided that the fractions differ by at least 0J. preferably by at least 0.5, more preferably by about 1.0.
  • the aspect ratio of Fraction 1 ⁇ aspect ration of Fraction 4 ⁇ the aspect ratio of Fraction 6.
  • the aspect ratio is [ ⁇ 110>/ ⁇ 011>] as discussed below in example 13.
  • the polymer produced according to this invention comprises 10-90 weight% of low molecular weight polymer (low is 50,000 or less preferably 40,000 or less), preferably 20 to 80 weight%, more preferably 40-60 weight%, based upon the weight of the polymer.
  • the polyolefin produced is found to have at least two species of molecular weights present at greater than 20 weight% based upon the weight of the polymer.
  • the polymer produced is bi- or multi- modal (on the SEC graph).
  • bi- or multi-modal is meant that the SEC graph of the polymer has two or more positive slopes, two or more negative slopes, and three or more inflection points (an inflection point is that point where the second derivative of the curve becomes negative) OR the graph has at least has one positive slope, one negative slope, one inflection point and a change in the positive and or negative slope greater than 20% of the slope before the change.
  • the SEC graph has one positive slope, one negative slope, one inflection point and an Mw/Mn of 10 or more, preferably 15 or more, more preferably 20 or more.
  • the SEC graph is generated by gel permeation chromatography on a waters 150 °C GPC instrument equipped with differential refraction index detectors.
  • the columns are calibrated by running a series of narrow polystyrene standards and the molecular weights were calculated using
  • the polyolefms then can be made into films, molded articles, sheets, pipes and the like.
  • the films may be formed by any of the conventional technique known in the art including extrusion, co-extrusion, lamination, blowing and casting.
  • the film may be obtained by the flat film or tubular process which may be followed by orientation in an uniaxial direction or in two mutually perpendicular directions in the plane of the film.
  • Particularly preferred methods to form the polymers into films include extrusion or coextrusion on a blown or cast film line.
  • the films produced may further contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, polymer processing aids, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents.
  • Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, BaSO 4 , diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, glass beads and the like.
  • the additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight %.
  • the films produced using the polymers of this invention have extremely good appearance properties.
  • the films have a low gel content and/or have good haze and gloss.
  • I 2 and I 21 are measured by ASTM 1238, Condition E and F.
  • MFR Melt Flow Ratio was measured by ASTM 1238.
  • BBF butyl branch frequency per 1000 carbon atoms
  • US Patent 5,521,152 was measured by infrared spectroscopy described in US Patent 5,521,152.
  • PDI polydispersity index
  • Mn and Mw were measured by gel permeation chromatography on a waters 150 °C GPC instrument equipped with differential refraction index detectors.
  • the GPC columns were calibrated by running a series of narrow polystyrene standards and the molecular weights were calculated using Mark Houwink coefficients for the polymer is question.
  • MI Melt Index
  • MIR Melt Index Ratio
  • Example 1 were charged to a 100 mL Schlenk tube equipped with a stir bar. The ligand was dissolved in 5 mL of toluene. To a second vessel equipped with a stir bar was charged 5.5 mmol (2.5g) tetrabenzyl zirconium and 10 mL toluene.
  • GC vial To an oven-dried, cooled, purged and sealed GC vial was charged 0J0 mL dried acetone. The GC vial was sealed in a shell vial and taken into the dry box. In a darkened room and darkened dry box 2.0 mmol (lJg) of the material made in Example 2 and 9 mL toluene were charged to 1 100 mL Schlenk flask equipped with a stir bar. To a second GC vial was charged 2.0 mmol (146 uL) acetone and 1.0 mL toluene.
  • the acetone/toluene solution was transferred dropwise via syringe into the stirred solution of [l-(2-pyridyl) N-l -methylethyl] [l-N-2,6- diisopropylphenylamido] zirconoum tribenzyl.
  • the vessel was covered with foil and allowed to stir at room temperature in the dry box overnight.
  • the reaction solution was vacuum stripped to a tacky orange residue. Dry hexane (20 mL) was added and the residue stirred vigorously, then vacuum stripped again to a yellow- orange glass. Hexane was added again and vigorously stirred.
  • the vessel was placed in a freezer (-24° C) for approximately 2 hours. The mixture was filtered through a medium porosity frit.
  • EXAMPLE 4 A series of bimodal ethylene/hexene copolymers were made in a laboratory scale, slurry phase reactor using mixed catalyst compositions of the complexes prepared in Example 2 and Example 3 according to the invention with modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number US 5,041,584).
  • MMAO modified methyl alumoxane
  • the catalyst composition was prepared by preparing mixtures of the complexes from Example 2 and Example 3 in toluene, and then contacting with MMAO solution (7.0 wt % Al in heptane) in the presence of 0J mL 1 -hexene.
  • Polymerization reaction conditions were 85° C, 85 psi (586 kPa) ethylene, 43 mL of 1-hexene, 0.5 micromole Zr, and a MMAO/Zr mole ratio of 1,000:1.
  • Complex ratios are expressed as the mole ratios of the complex prepared in Example 3 to the complex prepared in Example 2. Results are shown in Table 1 below.
  • An ethylene hexene copolymer was produced in a 14 inch (35.6cm) pilot plant gas phase reactor operating at 85 °C, 220 psi ( 1517 kPa) having a water cooled heat exchanger.
  • the ethylene was fed in at a rate of about 55 pounds of ethylene per hour (25kg/hr) and hexene was fed in at 1.4 pounds per hour(0.64 kg/hr) and hydrogen was fed in at rate of 0.021 pounds per hour (0.01 kg/hr) to make about 35 pounds per hour (15.9 kg/hr) of polymer.
  • Total reactor pressure was 350 psi (2413 kPa).
  • the nitrogen was present at about 3-7 pounds/hour (1.4 kg-3J kg).
  • the reactor was equipped with a plenum set at 1800 pounds per hour (818J kg/hr) with a single hole tapered nozzel injector having a 0.055 inch (0J4 cm) inside diameter.
  • the plenum is a device used to create a particle lean zone in a fluidized bed gas phase reactor.
  • This procedure was repeated and one or more of the reaction temperature, the Al/Zr ratio, the reaction temperature, the injection temperature or the hydrocarbon feed carrier were varied as reported in Table 2.
  • Wt% low Mw is the weight % of the lower molecular weight species produced as characterized by Size Exclusion Chromatography using a log normal Gaussian deconvolution.
  • Two ethylene hexene copolymers were produced in an 8 foot (2.4 m) diameter gas phase reactor (having a volume of about 2000 cubic feet) having a bed height of 38 feet(l 1.6 m).
  • the ethylene feed rate was about 8000 to 9000 pounds per hour (3636-4090 kg/hr).
  • the hexene feed rate was about 200-230 pounds per hour (90.0-104.5 kg/hr).
  • the hydrogen feed rate was about 1-2 pounds per hour (2.2 to 4.4 kg/hr).
  • the copolymer was produced at 8000-9000 pounds per hour(3636-4090 kg/hr). 30-60 pounds per hour of nitrogen (13.6-273 kg/hr) were fed into the reactor.
  • the reactor was equipped with a plenum set at 50,000 pounds per hour (22,121 kg/hr) and three hole nozzel having a diameter of 0J25 inches (0.32cm) tapering to a diameter of 0.05 inches (0J3cm) at the central hole and two other holes 0.30 inches ( 0J6 cm)from the nozzel end perpendicular to the flow of the gas and 5/64ths of an inch (OJOcm)wide.
  • the cycle gas velocity was about 2 -2.2 feet per sec (60-67 cm/sec).
  • the injection temperature was 22 °C for the first run and 80 ° C for the second run.
  • the catalyst was the catalyst produced in example 3 combined with 2 weight
  • Diethyl ketone (40 mmol, 4.0 mL, Aldrich, 3-Pentanone, 99.5%, [86.13] ) was dissolved in 96 mL of dry toluene.
  • the diethyl ketone solution was slowly transferred into a stirring solution (400 mL, 0J25M in toluene) of the complex prepared in Example 2.
  • the resulting solution was allowed to stir over night.
  • Methyl ethyl ketone (40 mmol, 3.6 mL, Aldrich, 2-Butanone, 99.5%,) was dissolved in 100 mL of dry toluene.
  • the methyl ethyl ketone solution was slowly transferred into a stirring solution (400 mL, 0J25M in toluene), of the complex prepared in Example 2.
  • the resulting solution was allowed to stir over night.
  • Example 2 In a dry box, 1 -hexene (0J mLs, alumina dried) was charged to an oven dried, 4 dram glass vial.
  • the complex from Example 2 (0.25 micromoles, 2.0 microliters , a 0J25M solution in toluene), and the complex prepared in Example 9 (0J5 ⁇ moles, 3.1 microliters, a 0.067M solution in deuterated benzene) was added to the
  • MMAO type 3 A (0J5 rnmoles) was then added to the vial resulting in a pale yellow reaction solution.
  • the reaction solution was charged to the reactor containing 600 mLs n-hexane, 43 mLs 1- hexene, and 0J3 mLs (0.25 mmoles) MMAO type 3 A, and run at 70°C, 85 psi ethylene, and 10 psi hydrogen for 30 minutes.
  • An ethylene hexene copolymer (A) having a density of about 0.946 g/cc was produced according to the procedure in example 5 except that the catalyst from example 3 was added at a rate of 9cc/hour and the catalyst from example 2 was fed at a rate of lcc/hour (90: 10 ratio). Hexene was fed at about 0.8-0.9 lbs (036-0.41 kg) per hour. Ethylene was fed at a rate of about 41 to 43 pounds (18.5-19.4kg) per hour. Hydrogen was fed at a rate of about 17-20 miliipounds (7J-9.1g) per hour and the hexane carrier was fed at a rate of about 100 cc/hour.
  • the ethylene partial pressure was 120 psi (827 kPa) and the reactor temperature was 75°C
  • the aluminum zirconium ratio was Al:Zr::300: 1.
  • Another ethylene hexene copolymer (B) was produced using the same procedure except that only the catalyst from example 3 was fed into the reactor (10 cc/br), the reactor temperature was 95 °C, hydrogen was fed at a rate of 12-14 millipounds (5.4-6.4g)per hour, the ethylene feed was fed at 41 to 45 pounds (18.5-203kg)per hour and the ethylene partial pressure was 220 psi(827kPa).
  • the copolymer had a density of 0.951 g/cc.
  • Another ethylene hexene copolymer (C) was produced using the same procedure except that only the catalyst from example 3 was fed into the reactor (12 cc/hr), the reactor temperature was 95 °C, hydrogen was fed at a rate of 12-13 millipounds (5.4-5.9g)per hour, the ethylene feed was fed at 44 to 47 pounds (19.9-21.2kg)per hour, the ethylene partial pressure was 220 psi(827kPa), and the hexane carrier was fed in at a rate of 70/cchr.
  • the copolymer had a density of 0.951 g/cc.
  • a Siemens GADDS X-ray diffraction (XRD) unit equipped with a Copper X-ray tube source ( ⁇ 1.54056 A) running at a power setting of 40 kV and 40 mA, a graphite monochrometer, a 0.3 mm collimator prior to the sample and a multi-wire General Area Diffraction Detector (GADD) with a sample-detector distance of 15 cm was the condition used for all data collection. Large individual particles were glued to a thin glass rod which allowed the particle to be suspended and rotated in the beam without any contribution from the glass rod or glue. Fine particles were placed in a thin silica capillary for the analysis.
  • XRD X-ray diffraction
  • the full profile curve fitting program supplied with the GADDS system was used for peak profile fitting to the spectra.
  • an air scatter pattern collected under the same conditions was subtracted from the experimental data prior to fitting, in the case of small particles a spectra combining the blank silica capillary and air scatter was subtracted from the experimental data prior to fitting.
  • diffraction peaks were fitted with a pseudo-voigt profile-shape-function with a mixing parameter of 1
  • amorphous peaks were fitted with a Lorentzian profile-shape- function with the FWHM (full width half maximum) of the peak and peak positions being fixed based upon amorphous scattering simulations
  • a paracrystalline component was fitted with a Pearson VII profile-shape-function with an exponent of 50 and (iv) a linear fit for the compton scattering.
  • the crystallite size was measured using the peak- width at half maximum intensity of the ⁇ 110 ⁇ and ⁇ 011 ⁇ reflections in X-ray diffraction patterns from granular polyethylene resm. These two values allow the size of the crystallite in the given crystallographic direction to be calculated using the Scherrer equation:
  • ⁇ is the wavelength of the incident X-ray
  • B' is the corrected peak width in radians at half maximum intensity (the instrumental beam broadening component was measured using a National Bureau of Standards SRM 660 Lanthanum Hexaboride sample)
  • ⁇ B is the peak position
  • t is the size of the crystal in the crystallographic direction based upon the reflection of interest.
  • the ⁇ 110> reflection provides crystallite size information in the ⁇ 110> direction that lies in the ab plane of the PE orthorhombic crystal
  • the ⁇ 011 ⁇ reflection provides crystallite size data in the ⁇ 011> direction which lies in the be plane which has a c- axis component, and therefore, information on the crystallite thickness can be obtained.
  • the magnitude of the crystallite size in these two directions can provide information on the crystallite morphology through a shape factor defined as ⁇ 110>/ ⁇ 01 1>.
  • the ratio is large, the crystals are large in the ab plane but thin in the be plane, hence they are "plate like," as the ratio approaches unity, both dimensions are similar and hence the crystallite morphology is more cuboidal or spherical in shape.
  • Table A provides X-ray diffraction data on all three samples studied. The degree of crystallinity was found not to change as a function of particle size, with the small particles having the same percent crystallinity as the much larger particles. The crystallite size in the ab plane was observed to decrease monotonically as particle size increased in both samples. Conversely, the crystallite size in the be plane (estimate of the c-axis component) was observed to increase monotonically as a function of particle size.
  • the observed behavior in this catalyst system is just one example of a graded microstructure.
  • the opposite structure could form with cuboidal/spherical crystallites at the center which then transition over to a more "plate-like" morphology.
  • An alternative crystallite morphology may be "rod-like" in which the shape factor becomes ⁇ 1.
  • the distribution of different crystallite morphologies could lead to a wide range of possible graded microstructures that could be controlled by the type of catalyst.
  • C and D CHMS is the high molecular weight species (over 500,000)
  • CLMS is the low molecular weight species (less than 3000)
  • VLD is very low density
  • LD low density
  • HD high Density
  • CCLDI crystalhzable chain length distribution index and is defined in US patent 5,698,427.
  • CDI (50) is composition distribution index that measures how much polymer is within 25 % of either side of the median.
  • CDI (100) is composition distribution index that measures how much polymer is within 50% of either side of the median. Both composition distributions are measured using the Temperature Rising Elution Fractionation (TREF) technique as described in Wild et al (J. Polym. Sci. Phys. Ed.
  • TEZ Temperature Rising Elution Fractionation
  • a dilute solution of the polymer in a solvent such as l,2,4-trichlorobenzene is loaded into a packed column at high temperature.
  • the column is allowed to cool slowly at 0.1 °C/min to ambient temperature.
  • the ethylene polymer is crystallized onto the packing in the order of increasing branching (decreasing crystallinity) with decreasing temperature.
  • the column is reheated at 0.7 °C/min, with a constant solvent flow through the column and the effluent is monitored with an infrared concentration detector.
  • CDI(100) and CDI(50) indices are similar to the "Composition Distribution
  • CDBI Breadth Index
  • CDBI is defined as the weigh percent of the copolymer chains having a comonomer content within 50% ( ⁇ 25%) of the median total molar comonomer content (see US patent 5,470,811).
  • the difference between the CDBI and the CDI(50) index is that the CDI(50) utilizes the mean branching frequency (or comonomer content) instead of the median comonomer content.
  • the CDI(50) is determined from the TREF data by converting the elution temperature to branching frequency as follows:
  • Branching frequency can be expressed as the average distance (in CH 2 units) between branches along the main polymer chain backbone or as the crystallizable chain length (L) where,
  • composition distribution index or crystalhzable chain length distribution index is then defined as:
  • CDI(50) is then calculated by determining the accumulative weight fraction contained within ⁇ 25% of BF.
  • CDI(IOO) is defined as the accumulative weight fraction contained within ⁇ 50% of BF.
  • a bimodal ethylene/hexene copolymer was made in a laboratory scale slurry phase reactor using the complex prepared in Example 3 according to the invention with
  • MMAO type 3A co-catalyst (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3 A, covered under patent number US 5,041 ,584).
  • MMAO3 A was allowed to react 4 hours in toluene with the complex prepared in Example 3 prior to conducting the polymerization reaction.
  • toluene (0.4mLs, alumina dried) was charged to an oven dried, 4 dram glass vial.
  • the complex prepared in Example 3 (2.0 micromoles, 0.067mL of an 0.030M solution in deuterated benzene) was added to the toluene resulting in a pale yellow solution.
  • MMAO type 3 A (1.0 mmoles, 0.52 mL, 1.89M,
  • the reactor was run at 85degrees C and at 85 psi (0.6MPa) ethylene for 30 minutes.
  • the SEC graph is presented as figure 8.
  • MMAO type 3A (5.8 mLs, 10 mmoles, 1.74M, 6.42 wt% in heptane) was charged to an oven dried, 4 dram glass vial. 2-methyl-l-phenyl-2- propanol(15.5 ⁇ Ls, 0J mmoles) was added to the MMAO dropwise while stirring resulting in a clear solution.
  • toluene (0J mLs, alumina dried) was charged to an oven dried, 4 dram glass vial.
  • the complex prepared in Example 2 (0.5 ⁇ moles, 6.3 microliters of an 0.080M solution in toluene) was added to the 1 -hexene resulting in a pale yellow solution.
  • the MMAO/ 2-methyl-l-phenyl-2-propanol solution prepared in the paragraph above (0.25 mmoles, 0J3 mL) was then added to the vial resulting in pale yellow reaction solution.
  • the vial was heated in an oil bath at 50°C for 5 minutes resulting in a reddish brown reaction solution.
  • the reaction solution was charged to a 1-L slurry reactor containing 600 mLs n- hexane, 43 mLs 1 -hexene, and 0J3 mLs (0J5 mmoles) MMAO/ 2-methyl-l- phenyl-2-propanol solution, and n at 85°C and 85 psi (0.6 MPa) ethylene for 30 minutes.
  • MMAO type 3A (5.8 mLs, 10 mmoles, 1.74M, 6.42 wt% in heptane) was charged to an oven dried, 4 dram glass vial.
  • Example 2 In a dry box, toluene (0J mLs, alumina dried) was charged to an oven dried, 4 dram glass vial.
  • the complex prepared in Example 2 (0.5 ⁇ moles, 6.3 microliters of an
  • the reaction solution was charged to a 1-L slurry reactor containing 600 mLs n- hexane, 43 mLs 1 -hexene, and 0J3 mLs (0.25 mmoles) MMAO/ 2-methyl-l- phenyl-2-propanol solution, and mn at 85°C and 85 psi (0.6MPa) ethylene for 30 minutes.

Abstract

L'invention concerne un système catalytique de polymérisation d'oléfine comprenant au moins un activateur et un parmi : a) au moins deux catalyseurs à métal de transition, à base de ligands bidentés contenant des parties pyridines ou quinoléines, représentés par les formules (I), (II), (III) ou (IV) ; b) le produit de la combinaison d'un activateur et d'un catalyseur à métal de transition à base de ligands bidentés contenant des parties pyridines ou quinoléines, telles que celles représentées par la formule (III) ou (IV), ayant été mis en réaction avant d'être introduits dans le réacteur, de préférence pendant au moins 15 minutes, et/ou c) le produit de la combinaison d'un additif et d'un catalyseur à métal de transition à base de ligands bidentés contenant des parties pyridines ou quinoléines, telles que celles représentées par la formule (I) ou (II). L'invention porte également sur un polymère produit à partir dudit système, notamment sur des résines de polyéthylène spéciales, et idéalement sur des résines de polyéthylène bimodales haute densité.
PCT/US1999/027502 1998-12-18 1999-11-19 Systeme catalytique de polymerisation d'olefine, procede de polymerisation et polymere ainsi obtenu WO2000037511A2 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU20272/00A AU756833B2 (en) 1998-12-18 1999-11-19 Olefin polymerization catalyst system, polymerization process and polymer therefrom
EP99963936A EP1144465A2 (fr) 1998-12-18 1999-11-19 Systeme catalytique de polymerisation d'olefine, procede de polymerisation et polymere ainsi obtenu
MXPA01006185A MXPA01006185A (es) 1998-12-18 1999-11-19 Sistema catalizador de polimerizacion de olefina de olefina, proceso de polimerizacion, y polimero del mismo.
BR9916313-6A BR9916313A (pt) 1998-12-18 1999-11-19 Sistema catalisador da polimerização da olefina, processo de polimerização e polìmero deste
PL99348825A PL348825A1 (en) 1998-12-18 1999-11-19 Olefin polymerization catalyst system, polymerization process and polymer therefrom
JP2000589580A JP2002533483A (ja) 1998-12-18 1999-11-19 オレフィン重合触媒システム、重合プロセス及びそれらからのポリマー
CA002350451A CA2350451A1 (fr) 1998-12-18 1999-11-19 Systeme catalytique de polymerisation d'olefine, procede de polymerisation et polymere ainsi obtenu
NO20012982A NO20012982L (no) 1998-12-18 2001-06-15 Olefinpolymerisasjonskatalysatorsystem, polymerisasjonsprosess og polymer derfra

Applications Claiming Priority (8)

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US09/213,627 US6320002B1 (en) 1997-07-02 1998-12-18 Olefin polymerization catalyst
US09/216,215 1998-12-18
US09/215,706 US6268447B1 (en) 1998-12-18 1998-12-18 Olefin polymerization catalyst
US09/216,163 US6265513B1 (en) 1997-07-02 1998-12-18 Polyolefin
US09/213,627 1998-12-18
US09/216,215 US6303719B1 (en) 1998-12-18 1998-12-18 Olefin polymerization catalyst system
US09/216,163 1998-12-18
US09/215,706 1998-12-18

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WO2002038628A2 (fr) * 2000-11-07 2002-05-16 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
KR100445185B1 (ko) * 2000-11-20 2004-09-13 충남대학교산학협력단 올레핀 중합용 촉매
US7094848B2 (en) 2003-05-13 2006-08-22 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system
CN1315876C (zh) * 2001-11-15 2007-05-16 尤尼威蒂恩技术有限责任公司 利用先行指标的聚合监测和控制
US7288596B2 (en) 2003-12-22 2007-10-30 Univation Technologies, Llc Polyethylene compositions having improved tear properties
EP2112175A1 (fr) 2008-04-16 2009-10-28 ExxonMobil Chemical Patents Inc. Activateur de métallocènes comprenant au moins un ligand hétérocyclique substitué par halogène, coordonné à un alumoxane
WO2011075258A1 (fr) * 2009-12-18 2011-06-23 Univation Technologies, Llc Procédés pour préparer des produits de polyoléfine ayant différentes propriétés de fluidification par cisaillement et trouble
WO2013070601A2 (fr) 2011-11-08 2013-05-16 Univation Technologies, Llc Procédés de préparation d'un système catalyseur
US9220322B2 (en) 2012-06-28 2015-12-29 Aba Hörtnagl Gmbh Tensioning apparatus
US9271545B2 (en) 2012-06-28 2016-03-01 Aba Hortnagl Gmbh Clamping apparatus for clamping at least one strap
US9332810B2 (en) 2011-01-03 2016-05-10 Aba Hörtnagl Gmbh Buckle
EP3309182A2 (fr) 2007-11-15 2018-04-18 Univation Technologies, LLC Catalyseurs de polymérisation, leurs procédés de fabrication, leurs procédés d'utilisation et produits polyoléfiniques fabriqués à partir de ceux-ci

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CN102453157B (zh) * 2010-10-22 2014-12-10 中国石油化工股份有限公司 用于在单一反应器中制备宽/双峰聚乙烯的催化剂体系
RU2598023C2 (ru) * 2011-05-13 2016-09-20 Юнивейшн Текнолоджиз, Ллк Полученные распылительной сушкой каталитические композиции и способы полимеризации, в которых они применяются

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WO1998049208A1 (fr) * 1997-04-25 1998-11-05 Bp Chemicals Limited Nouveaux composes et leur utilisation dans un procede de polymerisation
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Cited By (26)

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Publication number Priority date Publication date Assignee Title
US6750345B2 (en) 2000-11-07 2004-06-15 Symyx Technologies, Inc. Substituted pyridyl amine catalysts, complexes and compositions
WO2002046249A2 (fr) * 2000-11-07 2002-06-13 Symyx Technologies, Inc. Procedes de copolymerisation de l'ethylene et de isobutylene et polymeres ainsi obtenus
WO2002046249A3 (fr) * 2000-11-07 2003-02-13 Symyx Technologies Inc Procedes de copolymerisation de l'ethylene et de isobutylene et polymeres ainsi obtenus
WO2002038628A3 (fr) * 2000-11-07 2003-05-22 Symyx Technologies Inc Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
US6713577B2 (en) 2000-11-07 2004-03-30 Symyx Technologies, Inc. Substituted pyridyl amine catalysts and processes for polymerizing and polymers
US6727361B2 (en) 2000-11-07 2004-04-27 Symyx Technologies, Inc. Phosphino substituted pyridine amine ligands
US6828397B2 (en) 2000-11-07 2004-12-07 Symyx Technologies, Inc. Methods of copolymerizing ethylene and isobutylene and polymers made thereby
US6900321B2 (en) 2000-11-07 2005-05-31 Symyx Technologies, Inc. Substituted pyridyl amine complexes, and catalysts
US7018949B2 (en) 2000-11-07 2006-03-28 Symyx Technologies, Inc. Substituted pyridyl amine catalysts and processes for polymerizing and polymers
US7087690B2 (en) 2000-11-07 2006-08-08 Symyx Technologies, Inc. Substituted pyridyl amine catalysts and processes for polymerizing crystalline polymers
WO2002038628A2 (fr) * 2000-11-07 2002-05-16 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
KR100445185B1 (ko) * 2000-11-20 2004-09-13 충남대학교산학협력단 올레핀 중합용 촉매
CN1315876C (zh) * 2001-11-15 2007-05-16 尤尼威蒂恩技术有限责任公司 利用先行指标的聚合监测和控制
US7094848B2 (en) 2003-05-13 2006-08-22 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system
US7285609B2 (en) 2003-05-13 2007-10-23 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system useful for polar monomers
US7479531B2 (en) 2003-05-13 2009-01-20 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system useful for polar monomers
US7288596B2 (en) 2003-12-22 2007-10-30 Univation Technologies, Llc Polyethylene compositions having improved tear properties
US7560516B2 (en) 2003-12-22 2009-07-14 Univation Technologies, Llc Polyethylene compositions having improved tear properties
EP3309182A2 (fr) 2007-11-15 2018-04-18 Univation Technologies, LLC Catalyseurs de polymérisation, leurs procédés de fabrication, leurs procédés d'utilisation et produits polyoléfiniques fabriqués à partir de ceux-ci
EP2112175A1 (fr) 2008-04-16 2009-10-28 ExxonMobil Chemical Patents Inc. Activateur de métallocènes comprenant au moins un ligand hétérocyclique substitué par halogène, coordonné à un alumoxane
WO2011075258A1 (fr) * 2009-12-18 2011-06-23 Univation Technologies, Llc Procédés pour préparer des produits de polyoléfine ayant différentes propriétés de fluidification par cisaillement et trouble
US8637615B2 (en) 2009-12-18 2014-01-28 Univation Technologies, Llc Methods for making polyolefin products having different shear thinning properties and haze
US9332810B2 (en) 2011-01-03 2016-05-10 Aba Hörtnagl Gmbh Buckle
WO2013070601A2 (fr) 2011-11-08 2013-05-16 Univation Technologies, Llc Procédés de préparation d'un système catalyseur
US9220322B2 (en) 2012-06-28 2015-12-29 Aba Hörtnagl Gmbh Tensioning apparatus
US9271545B2 (en) 2012-06-28 2016-03-01 Aba Hortnagl Gmbh Clamping apparatus for clamping at least one strap

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CN1335860A (zh) 2002-02-13
CZ20012224A3 (cs) 2001-09-12
WO2000037511A3 (fr) 2000-11-09
BR9916313A (pt) 2001-10-02
NO20012982L (no) 2001-08-14
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CN1241953C (zh) 2006-02-15
NO20012982D0 (no) 2001-06-15

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