WO1998030603A1 - A process for polymerizing olefins - Google Patents

A process for polymerizing olefins Download PDF

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Publication number
WO1998030603A1
WO1998030603A1 PCT/NL1997/000696 NL9700696W WO9830603A1 WO 1998030603 A1 WO1998030603 A1 WO 1998030603A1 NL 9700696 W NL9700696 W NL 9700696W WO 9830603 A1 WO9830603 A1 WO 9830603A1
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Prior art keywords
hydrogen
cocatalyst
group
olefins
transition metal
Prior art date
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Ceased
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PCT/NL1997/000696
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English (en)
French (fr)
Inventor
Maurits Frederik Hendrik Van Tol
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Koninklijke DSM NV
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DSM NV
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Filing date
Publication date
Priority claimed from NL1004991A external-priority patent/NL1004991C2/nl
Application filed by DSM NV filed Critical DSM NV
Priority to AU53475/98A priority Critical patent/AU5347598A/en
Priority to AT97950491T priority patent/ATE272078T1/de
Priority to EA199900650A priority patent/EA199900650A1/ru
Priority to JP53077198A priority patent/JP2002514247A/ja
Priority to EP97950491A priority patent/EP0954540B1/en
Priority to CA002277886A priority patent/CA2277886A1/en
Priority to DE69730047T priority patent/DE69730047T2/de
Publication of WO1998030603A1 publication Critical patent/WO1998030603A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/30—Germanium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • 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
    • 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
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 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
    • C08F4/61925—Component covered by group C08F4/60 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 non-bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the invention relates to a process for polymerizing olefins by bringing olefins into contact with a transition metal catalyst and a cocatalyst.
  • the polymerization of olefins usually requires the use of not only a transition metal catalyst, but also the use of a cocatalyst to obtain an active catalyst system.
  • Ziegler-Natta catalysts have been used for the polymerization of olefins. If olefin polymerizations are to proceed satisfactory with these Ziegler-Natta catalysts, it is necessary to add cocatalysts. Aluminium-containing cocatalysts such as, for example, diethylaluminium chloride, are often used in combination with Ziegler-Natta catalysts.
  • transition metal catalysts such as, for example, metallocene catalysts have also been used for the polymerization of olefins. If olefin polymerizations using metallocene catalysts are to proceed satisfactory it is likewise necessary to use a cocatalyst.
  • cocatalysts often used in combination with metallocene catalysts are aluminoxanes .
  • An example of an aluminoxane is methyl- aluminoxane (MAO) .
  • the use of aluminoxanes as a cocatalyst in the polymerization of olefins with the aid of a metallocene catalyst has the drawback that a very large excess of the aluminoxane with respect to the metallocene catalyst has to be used in order to obtain an active catalyst system. Consequently, the polyolefin produced contains a high aluminium concentration, and as a result it is often necessary for the aluminium to be washed out from the polyolefin. It is an object of the invention to provide cocatalysts which can be used in conjunction with a transition metal catalyst for the polymerization of olefins, which do not have this drawback. 5
  • the invention relates to a cocatalyst in accordance with formula
  • XR 4 wherein X is Si, Ge, Sn or Pb,
  • R is hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group and wherein at least one R group is not hydrogen and contains one or more halogen atoms, or to a cocatalyst in accordance with the formula [XR 5 ] ⁇ [Y] ⁇ , wherein
  • R is hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group and wherein at least one R group is not hydrogen and contains one or more halogen atoms, and Y is a cation.
  • Lewis acids are boranes such as, for example, tris (pentafluorophenyl) borane, and examples of ion complexes are borates such as, for example, dimethylanilinium tetrakis (pentafluorophenyl) borate,
  • a further advantage of the use of the compounds according to the invention as a cocatalyst in the polymerization of olefins is that using these compounds is cheaper, as a rule, than using aluminoxanes, boranes or borates.
  • X is an atom from group 14 of the Periodic Table of the Elements and can be selected from Si, Ge, Sn and P .
  • X is Si, because Si is not toxic.
  • the R groups may be identical or different and can be selected from hydrogen and alkyl, aryl, arylalkyl or alkylaryl groups .
  • At least one R group is not hydrogen and contains one or more halogen atoms. This implies that in a compound in accordance with the formula XR 4 or in accordance with the formula [XR 5 ] " [Y] + at least one halogen atom is present which does not form part of the cation Y.
  • the R group is a hydrocarbon group containing 1-20 carbon atoms.
  • R groups are methyl, ethyl, propyl, isopropyl, hexyl, decyl and phenyl.
  • Two R groups may together form a bridged R 2 group such as, for example, a biphenyl- 2,2'-diyl group and a diphenyl-2, 2' -diylmethane group.
  • R groups may contain one or more halogen atoms .
  • Halogen atoms are F, Cl, Br and I.
  • Combina- tions of different halogen atoms may be present in one R group or distributed over various R groups .
  • R groups containing a halogen atom are chloromethyl, 1, 2-dibromoethyl, pentafluorophenyl and octafluorobiphenyl-2 , 2 ' -diyl .
  • At least 2 R groups together form a bridged aryl group.
  • the compound in accordance with the formula XR 4 or [XR 5 ] " [Y] + contains octafluorobiphenyl - 2,2'-diyl groups .
  • the cation Y is, for example, a Br ⁇ nsted acid which is able to donate a proton, a cation of an alkali metal or a carbene .
  • cations are Li + , K + , Na + , H + , triphenylcarbenium, anilinium, guanidinium, glycinium, ammonium or a substituted ammonium cation in which at most 3 hydrogen atoms have been replaced by a hydrocarbyl radical having 1-20 carbon atoms, or a substituted hydrocarbyl radical having 1-20 carbon atoms, in which 1 or more of the hydrogen atoms have been replaced by a halogen atom, phosphonium radicals, substituted phosphonium radicals, in which at most 3 hydrogen atoms have been replaced by a hydrocarbyl radical having 1-20 carbon atoms or a substituted hydrocarbyl radical having 1-20 carbon atoms, in which 1 or more of the hydrogen atoms have been replaced by a
  • Suitable carrier materials to be mentioned are Si0 2 , A1 2 0 3 , MgCl 2 and polymer particles such as polystyrene beads. These carrier materials may also be modified with, for example, silanes and/or aluminoxanes and/or aluminiumalkyls .
  • the supported cocatalysts can be synthesized prior to the polymerization but can also be formed in situ.
  • transition metal catalysts can be used as a catalyst for the polymerization of olefins. Examples of such catalysts are described, for example, in US-A-5 , 096 , 867 , O-A-92/00333 , EP-A-
  • Transition metal catalysts containing metals from group 3 of the Periodic Table of the Elements and the lanthanides can likewise be used.
  • Supported transition metal catalysts can also be used.
  • Suitable carrier materials to be mentioned are Si0 2 , A1 2 0 3 , MgCl 2 and polymer particles such as polystyrene beads. These carrier materials may also be modified with, for example, silanes and/or aluminoxanes and/or aluminiumalkyls .
  • the supported transition metal catalysts may be synthesized prior to the polymerization but may also be formed in situ.
  • Metallocene catalysts for the polymerization of olefins in combination with a cocatalyst according to the invention.
  • Metallocene catalysts are characterized by the presence of one or more ⁇ -bound ligands such as, for example, cyclopentadiene (Cp) ligands or ligands related to cyclopentadiene, such as, for example, indene and fluorene, in the transition metal catalyst. More preference is given to the use of a transition metal catalyst in which the transition metal is in a reduced oxidation state, as described in 0-A-96/13529.
  • olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes
  • olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes
  • the above-described catalyst system can equally be used for the polymerization of vinylaromatic monomers such as, for example, styrene and p-methylstyrene, for the polymerization of polar vinyl monomers such as, for example, monomers containing alcohol, amine, alkyl halide, ether, amide, imine or anhydride groups, and for the polymerization of cyclic olefins such as, for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, dimethano- octahydronaphthalene and substituted norbornenes .
  • vinylaromatic monomers such as, for example, styrene and p-methylstyrene
  • polar vinyl monomers such as, for example, monomers containing alcohol, amine, alkyl halide, ether, amide, imine or anhydride groups
  • the amount of cocatalyst used is normally 1:100-1000:1, preferably 1:5-250:1.
  • the polymerizations can be carried out in the manner known for this purpose, and the use of the cocatalyst according to the invention does not require any significant adaptation of these methods.
  • the polymerizations can be carried out in suspension, solution, emulsion, gas phase or as a bulk polymerization.
  • the transition metal catalyst or the cocatalyst according to the invention is preferable for the transition metal catalyst or the cocatalyst according to the invention to be used on a carrier material.
  • both the catalyst and the cocatalyst can be used on a carrier material.
  • the polymerizations are carried out at temperatures of between -50°C and +350°C, preferably between 50°C and 250°C. Pressures employed generally are between atmospheric pressure and 250 MPa, for bulk polymerizations more particularly between 50 and 250 MPa, for the other polymerization processes between 0.5 and 25 MPa.
  • Dispersing agents and solvents which can be employed include, for example, substituted and unsubstituted hydrocarbons such as pentane, heptane and mixtures thereof. Aromatic, possibly perfluorinated hydrocarbons, may also be used. Equally, a monomer to be used in the polymerization can be employed as a dispersing agent.
  • M D is molecular weight distribution, defined as Mw/Mn. Unless stated otherwise Mz, Mw and Mn are molecular weights determined using universal calibration procedure in SEC-DV measurements.
  • Dry petrol 50 ml was again added to yield a light orange pink coloured slurry; letting slurry settle yielded a light orange coloured petrol and a light yellow precipitate.
  • the petrol was evaporated to yield a light orange coloured solid.
  • a toluene extraction was done 2 times to separate the cation anion complex from LiCl; the evaporation of toluene yielded a light pink solid.
  • Petrol extraction was done 2 times to extract any unreacted triphenylchloromethane .
  • the catalyst/cocatalyst mixture was introduced.
  • the ethylene pressure was kept constant at 20 bars during the polymerisation.
  • the polymerization which showed a rather constant activity prophile in time, was stopped, the polymer was removed from the reactor and the yield was determined to be 10.51 g.
  • Example III The polymerisation described under example Id was repeated but the polymerisation time was elongated to 60 minutes. The system remained active all the time and the polymer yield appeared to be 37.1 g.
  • the example Id was repeated at a temperature of 160°C during 10 minutes with a different transition metal compound: (Cp*) C 2 H 4 (N(CH 3 ) 2 ) TiCl 2 , where Cp* stands for a cyclopentadienyl ring with four methyl groups ,
  • C 2 H 4 is an ethylene bridge, bridging the Cp* to a
  • the polymer yield was 7.4 g.
  • Example VII The polymerisation described under example Id was repeated but now with the catalyst bis (2- methylindenyl) dimethyl zirconium and cocatalyst of example Ic) at a temperature of 100°C for 15 minutes. The polymer yield was 0.5 g.
  • the solid was washed 3 times with dry petrol and dried under vacuum to yield an off-white solid.
  • Example X The example IX was repeated, but now with the transition metal complex bis (pentamethylcyclopenta- dienyl) dimethylzirconium.
  • the polymer yield was 3.3 g.
  • Ethylmagnesiumbromide (6.8 ml, 6.8 mmol) was added to 2H, 2' H-Octafluorobiphenyl (1.0 g, 3.4 mmol) in dry tetrahydrofuran (50 ml) at -78°C. The reaction was warmed to room temperature slowly. The reaction mixture became a clear yellow solution.
  • the reaction was cooled to -78°C.
  • the reaction mixture obtained a non-clear yellow colour.
  • the reaction was warmed to room temperature slowly.
  • the white solid was washed one time with petrol and dried under vacuum.
  • Methyllithium (553 ⁇ l, 0.819 mmol) was added to bis (octafluorobiphenyl) silane (507.7 mg, 0.819 mmol) in dry tetrahydrofuran (40 ml) at -78°C. The reaction mixture was warmed slowly to room temperature, no colour change was observed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/NL1997/000696 1997-01-14 1997-12-15 A process for polymerizing olefins Ceased WO1998030603A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU53475/98A AU5347598A (en) 1997-01-14 1997-12-15 A process for polymerizing olefins
AT97950491T ATE272078T1 (de) 1997-01-14 1997-12-15 Verfahren zur olefinpolymerisation
EA199900650A EA199900650A1 (ru) 1997-01-14 1997-12-15 Способ полимеризации олефинов
JP53077198A JP2002514247A (ja) 1997-01-14 1997-12-15 オレフィンの重合法
EP97950491A EP0954540B1 (en) 1997-01-14 1997-12-15 A process for polymerizing olefins
CA002277886A CA2277886A1 (en) 1997-01-14 1997-12-15 A process for polymerizing olefins
DE69730047T DE69730047T2 (de) 1997-01-14 1997-12-15 Verfahren zur olefinpolymerisation

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL1004991 1997-01-14
NL1004991A NL1004991C2 (nl) 1997-01-14 1997-01-14 Toepassing van verbindingen die Si, Ge, Sn of Pb bevatten als cokatalysator bij de polymerisatie van olefinen.
US3816097P 1997-02-13 1997-02-13
US60/038,160 1997-02-13

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WO1998030603A1 true WO1998030603A1 (en) 1998-07-16

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US (1) US6218487B1 (https=)
EP (1) EP0954540B1 (https=)
JP (1) JP2002514247A (https=)
CN (1) CN1248979A (https=)
AT (1) ATE272078T1 (https=)
AU (1) AU5347598A (https=)
CA (1) CA2277886A1 (https=)
DE (1) DE69730047T2 (https=)
ES (1) ES2226005T3 (https=)
WO (1) WO1998030603A1 (https=)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004046214A2 (en) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
WO2005113622A1 (en) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
WO2006049699A1 (en) 2004-10-29 2006-05-11 Exxonmobil Chemical Patents Inc Catalyst compound containing divalent tridentate ligand
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
WO2010071798A1 (en) 2008-12-18 2010-06-24 Univation Technologies, Llc Method for seed bed treatment for a polymerization reaction
WO2011048527A1 (en) 2009-10-19 2011-04-28 Sasol Technology (Pty) Limited Oligomerisation of olefinic compounds with reduced polymer formation
WO2012074709A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc Processes for the polymerization of olefins with extracted metal carboxylate salts
WO2012074710A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc. Catalyst composition having improved flow characteristics and methods of making and using the same
WO2012158260A1 (en) 2011-05-13 2012-11-22 Univation Technologies, Llc Spray-dried catalyst compositions and polymerization processes employing the same
WO2014109832A1 (en) 2013-01-14 2014-07-17 Univation Technologies, Llc Methods for preparing catalyst systems with increased productivity
WO2014120494A1 (en) 2013-01-30 2014-08-07 Univation Technologies, Llc Processes for making catalyst compositions having improved flow
WO2015049034A1 (de) * 2013-10-04 2015-04-09 Merck Patent Gmbh Perfluoralkylfluor- oder perfluoralkylchlorgermanate
WO2015153082A1 (en) 2014-04-02 2015-10-08 Univation Technologies, Llc Continuity compositions and methods of making and using the same
WO2016145179A1 (en) 2015-03-10 2016-09-15 Univation Technologies, Llc Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes
WO2016172110A1 (en) 2015-04-20 2016-10-27 Univation Technologies, Llc Bridged bi-aromatic ligands and transition metal compounds prepared therefrom
WO2016172097A1 (en) 2015-04-20 2016-10-27 Univation Technologies, Llc Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom
WO2016176135A1 (en) 2015-04-27 2016-11-03 Univation Technologies, Llc Supported catalyst compositions having improved flow properties and preparation thereof
EP3372311A1 (en) 2007-10-22 2018-09-12 Univation Technologies, LLC Film comprising a polyethylene composition having improved properties

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ATE469670T1 (de) * 2002-12-09 2010-06-15 Medtronic Inc Verbindungsmodul für eine modulare implantierbare medizinische vorrichtung
US7119153B2 (en) * 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
JP6914348B2 (ja) 2017-03-06 2021-08-04 ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ オレフィン重合のためのチーグラー−ナッタ触媒調製用の電子供与体及び触媒系

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WO2004046214A2 (en) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
WO2005113622A1 (en) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
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EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
EP3372311A1 (en) 2007-10-22 2018-09-12 Univation Technologies, LLC Film comprising a polyethylene composition having improved properties
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WO2012074709A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc Processes for the polymerization of olefins with extracted metal carboxylate salts
WO2012074710A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc. Catalyst composition having improved flow characteristics and methods of making and using the same
WO2012158260A1 (en) 2011-05-13 2012-11-22 Univation Technologies, Llc Spray-dried catalyst compositions and polymerization processes employing the same
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WO2015049034A1 (de) * 2013-10-04 2015-04-09 Merck Patent Gmbh Perfluoralkylfluor- oder perfluoralkylchlorgermanate
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WO2016172110A1 (en) 2015-04-20 2016-10-27 Univation Technologies, Llc Bridged bi-aromatic ligands and transition metal compounds prepared therefrom
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WO2016176135A1 (en) 2015-04-27 2016-11-03 Univation Technologies, Llc Supported catalyst compositions having improved flow properties and preparation thereof

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AU5347598A (en) 1998-08-03
EP0954540B1 (en) 2004-07-28
DE69730047T2 (de) 2005-07-21
DE69730047D1 (de) 2004-09-02
EP0954540A1 (en) 1999-11-10
ATE272078T1 (de) 2004-08-15
ES2226005T3 (es) 2005-03-16

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