WO1998006759A1 - Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization - Google Patents
Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization Download PDFInfo
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- WO1998006759A1 WO1998006759A1 PCT/US1997/013793 US9713793W WO9806759A1 WO 1998006759 A1 WO1998006759 A1 WO 1998006759A1 US 9713793 W US9713793 W US 9713793W WO 9806759 A1 WO9806759 A1 WO 9806759A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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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
- C07F17/00—Metallocenes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
- C08F2420/00—Metallocene catalysts
- C08F2420/08—Heteroatom bridge, i.e. Cp or analog where the bridging atom linking the two Cps or analogs is a heteroatom different from Si
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63908—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
Definitions
- ZAM Zinc Ansa Metallocene
- the present invention generally relates to olefin polymerization catalysts, and more specifically to single component metallocene catalysts for ⁇ -olefin polymerization.
- catalysts require an anionic co-catalyst (or a catalyst activator) , typically perfluorophenylborates or methyl aluminoxane (MAO) , to generate the catalytically active cationic fourteen electron d° species .
- anionic co-catalyst typically perfluorophenylborates or methyl aluminoxane (MAO)
- MAO-based systems predominate in industrial applications.
- MAO must be present in large molar excess (200-2000 times that of the metallocene catalyst) , its presence accounts for over 50% of the cost of the catalytic system. In addition to the increased expense, little is known about MAO's structure or role in the polymerization reaction. Moreover, because MAO may also provide an additional route for chain termination (via chain transfer to the trimethyl aluminum) , this complicates the design of more selective catalysts.
- Another approach is to incorporate a counter anion for a Group IV catalyst directly into the ligand.
- Jordan, et al . (Crowther, et al . , J. Am. Chem. Soc . 113:1455 (1991)) prepared catalyst in which one cyclopentadienyl (Cp) ligand is replaced by a dianionic dicarbolide ligand.
- Cp cyclopentadienyl
- the resulting complex was expected to be capable of ⁇ -olefin polymerization.
- these complexes readily undergo ⁇ - elimination, have low activity, and only oligomerize polypropylene.
- Figure 1 illustrates the result of energy calculations comparing a zwitterion ansa metallocene (ZAM) catalyst with a standard Ziegler-Natta catalyst for each step of olefin polymerization.
- ZAM zwitterion ansa metallocene
- Figure 2 illustrates transition state enthalpies for two ZAM catalysts and a standard Ziegler-Natta catalyst .
- ZAM zwitterion ansa metallocene
- M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
- E is boron or aluminum;
- R-_ and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
- Ri ⁇ are eacn independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
- R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl , hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C ⁇ to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
- each pair of adjacent radicals on the cyclopentadienyl rings (e.g., R 4 and R 5 or R 10 and R ⁇ ⁇ ) together may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
- M is a Group IV metal
- R x and R 2 are each an electron withdrawing group
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l ⁇ are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
- M is zirconium.
- the invention further includes a efhod for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the type described above.
- the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
- the catalysts of the present invention are zwitterion ansa metallocenes that are referred to as ZAM catalysts.
- the inventive catalysts eliminates the need for a counterion like MAO while retaining or improving most of the various kinetic steps in olefin polymerization over prior art Ziegler-Natta catalysts.
- ZAM catalysts are of the general formula:
- M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
- E is boron or aluminum;
- R ⁇ and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C 1 to C 10 alkoxy;
- R ⁇ are eacn independently selected from a group consisting of hydrogen, substituted or unsubstituted C 2 to C 10 alkyl, substituted or unsubstituted C ⁇ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and, R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cycl
- each pair of adjacent radicals on the cyclopentadienyl rings may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
- Examples of compounds wherein one or more pairs of adjacent radicals form cyclic ring include but are not limited to:
- R-_ and R 2 are each a group which increases the electrophilicity of the metal center.
- suitable groups include but are not limited to F, C 6 F 5 , and CF 3 .
- M is a Group IV metal
- R 3 , R 4 , R 5 , R 6 , R E R g , R 10' and R 12 are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
- M is zirconium.
- E is boron or aluminum
- R x and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C-_ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C x to C 10 alkoxy;
- R 3 , R 4 , R 5 , and R 6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 9 ) 3 where R 9 is selected from the group consisting of ⁇ to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
- R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted C to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 10 ) 3 where R 10 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
- R 8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl , hydride, and Si(R 11 ) 3 where R ⁇ is selected from a group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
- R 7 is tert-butyl or trimethyl-silyl .
- These compounds are variations of traditional metallocene catalysts and are generally referred to as mono-Cp "constrained- geometry catalysts" (or CGC) .
- CGC constrained- geometry catalysts
- the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the types described above.
- the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the 'catalyst in the presence of a solvent .
- the constrained-geometry embodiment of the present invention may be synthesized by known methods in the art, including but not limited to the protocol described by Organome tallies, 9: 866-869 (1990) which is incorporated herein by reference.
- the metallocene catalysts of the present invention may also be prepared by a variety of methods known in the art including the protocol described below. Although the protocol is for the preparation of (C 6 F 5 ) 2 B (C 5 H 4 ) 2 ZrCH 3 , persons skilled in the art would readily know how to adapt the protocol for the various inventive embodiments.
- THF tetrahydrofuran
- Density Functional Theory (DFT) calculations were carried out using the PS-GVB-DFT program. Ringnalda, et al . , PS-GVB, 2.3 Schr ⁇ dinger, Inc. 1996; Slater, J. C. , Quantum Theory of Molecules and Solids, vol , 4 . The Self -Consistent Field for Mol ecules and Solids (McGraw-Hill, New York, 1974) ; and Perdew, J. P. Electronic Structure Theory of Solids, Ziesche, P. & Eschrig, H. eds. (Akademie Verlag, Berlin, 1991) .
- the Zr was described with the LACVP Hay adt effective core potential (ECP) to replace the core electrons [leaving the (4s) 2 (4p) 6 [ (4d) (5s) (5p)] 4 electrons to be described explicitly] and using the standard double zeta contraction.
- ECP effective core potential
- the results of the insertion reaction are summarized in Figure 1 which displays the energies along the reaction coordinates for ZAM I and control II.
- Figure 1 illustrates, the standard cationic metallocene binds ethylene exothermically by approximately 23 kcal/mol while the corresponding ZAM binds exothermically by about 16 kcal/mol.
- the insertion barrier for the cationic metallocene ranges from about 6-10 kcal/mol while ZAM has an insertion barrier of just less than 3 kcal/mol.
- the remaining energies of the ZAM catalyst were consistent with the energies of the cationic catalyst at the same level of theory.
- the energetics for the insertion reaction for ZAM I, ZAM III and control II are summarized in figure 2.
- the results for ZAM I and control II were calculated using DLDA-B3LYP and are consistent with the results using NLDA-GGAII.
Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP97938137A EP0920455B1 (en) | 1996-08-09 | 1997-08-08 | Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization |
DE69723084T DE69723084T2 (en) | 1996-08-09 | 1997-08-08 | CATALYST BASED ON A ZWITTERIONIC ANSA METALLOCENS OF GROUP IV FOR THE POLYMERIZATION OF ALPHA OLEFINS |
AU40532/97A AU4053297A (en) | 1996-08-09 | 1997-08-08 | Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization |
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US2439596P | 1996-08-09 | 1996-08-09 | |
US60/024,395 | 1996-08-09 | ||
US08/907,395 | 1997-08-07 | ||
US90739598A | 1998-01-01 | 1998-01-01 |
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WO1998006759A1 true WO1998006759A1 (en) | 1998-02-19 |
WO1998006759A9 WO1998006759A9 (en) | 1998-06-25 |
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Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2001058912A1 (en) * | 2000-02-11 | 2001-08-16 | The Dow Chemical Company | Dinuclear group 4 metal boron or aluminum bridge containing ansa-complexes |
WO2001068719A1 (en) * | 2000-03-14 | 2001-09-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Transition metal catalyst component for polymerization and process for producing polymer with the same |
WO2002034759A1 (en) * | 2000-10-24 | 2002-05-02 | Dow Global Technologies Inc. | Bridged ylide group containing metal complexes |
WO2002076999A1 (en) * | 2001-03-23 | 2002-10-03 | Bayer Aktiengesellschaft | Catalysts characterized by a donor-acceptor interaction |
WO2004094487A1 (en) | 2003-03-21 | 2004-11-04 | Dow Global Technologies, Inc. | Morphology controlled olefin polymerization process |
US6891004B2 (en) | 2000-03-14 | 2005-05-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Transition metal catalyst component for polymerization, and method for producing a polymer by means thereof |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
US7456244B2 (en) | 2006-05-23 | 2008-11-25 | Dow Global Technologies | High-density polyethylene compositions and method of making the same |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
WO2010088265A1 (en) | 2009-01-30 | 2010-08-05 | Dow Global Technologies Inc. | High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices |
EP2218751A1 (en) | 2004-12-17 | 2010-08-18 | Dow Global Technologies Inc. | Rheology modified polyethylene compositions |
US7981517B2 (en) | 2007-08-28 | 2011-07-19 | Dow Global Technologies Inc. | Bituminous compositions and methods of making and using same |
US8445594B2 (en) | 2006-05-02 | 2013-05-21 | Dow Global Technologies Llc | High-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles |
WO2014105614A1 (en) | 2012-12-28 | 2014-07-03 | Univation Technologies, Llc | Methods of integrating aluminoxane production into catalyst production |
WO2014109832A1 (en) | 2013-01-14 | 2014-07-17 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
WO2016182920A1 (en) | 2015-05-08 | 2016-11-17 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2019118073A1 (en) | 2017-12-13 | 2019-06-20 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization process |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
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Cited By (38)
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---|---|---|---|---|
WO2001058912A1 (en) * | 2000-02-11 | 2001-08-16 | The Dow Chemical Company | Dinuclear group 4 metal boron or aluminum bridge containing ansa-complexes |
WO2001068719A1 (en) * | 2000-03-14 | 2001-09-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Transition metal catalyst component for polymerization and process for producing polymer with the same |
US6891004B2 (en) | 2000-03-14 | 2005-05-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Transition metal catalyst component for polymerization, and method for producing a polymer by means thereof |
JP4819279B2 (en) * | 2000-03-14 | 2011-11-24 | 電気化学工業株式会社 | Transition metal catalyst component for polymerization and method for producing polymer using the same |
WO2002034759A1 (en) * | 2000-10-24 | 2002-05-02 | Dow Global Technologies Inc. | Bridged ylide group containing metal complexes |
WO2002076999A1 (en) * | 2001-03-23 | 2002-10-03 | Bayer Aktiengesellschaft | Catalysts characterized by a donor-acceptor interaction |
US6657027B2 (en) | 2001-03-23 | 2003-12-02 | Bayer Aktiengesellschaft | Catalysts with a donor-acceptor interaction |
WO2004094487A1 (en) | 2003-03-21 | 2004-11-04 | Dow Global Technologies, Inc. | Morphology controlled olefin polymerization process |
EP2218751A1 (en) | 2004-12-17 | 2010-08-18 | Dow Global Technologies Inc. | Rheology modified polyethylene compositions |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
US8445594B2 (en) | 2006-05-02 | 2013-05-21 | Dow Global Technologies Llc | High-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles |
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