WO1998006759A1 - Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines - Google Patents

Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
unsubstituted
aryl
alkyl
Prior art date
Application number
PCT/US1997/013793
Other languages
English (en)
Other versions
WO1998006759A9 (fr
Inventor
William A. Goddard, Iii
Christopher G. Brandow
Original Assignee
California Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by California Institute Of Technology filed Critical California Institute Of Technology
Priority to EP97938137A priority Critical patent/EP0920455B1/fr
Priority to DE69723084T priority patent/DE69723084T2/de
Priority to AU40532/97A priority patent/AU4053297A/en
Publication of WO1998006759A1 publication Critical patent/WO1998006759A1/fr
Publication of WO1998006759A9 publication Critical patent/WO1998006759A9/fr

Links

Classifications

    • 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
    • B01J31/16—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
    • 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
    • B01J31/16—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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Des catalyseurs métallocènes à un seul composant pour la polymérisation d'α-oléfine sont décrits. Les catalyseurs métallocènes cationiques de l'art antérieur requièrent un co-catalyseur anionique séparé tel que l'aluminoxane de méthyl (MAO). Cependant, en raison de leur fonctionnalité 'intégrée' co-catalyseur anionique, les catalyseurs zwittérion ansa métallocène (ZAM) n'ont pas besoin d'un co-catalyseur anionique séparé.
PCT/US1997/013793 1996-08-09 1997-08-08 Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines WO1998006759A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97938137A EP0920455B1 (fr) 1996-08-09 1997-08-08 Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines
DE69723084T DE69723084T2 (de) 1996-08-09 1997-08-08 Katalysator auf basis eines zwitterionischen ansa metallocens der gruppe iv für die polymerisation von alpha-olefinen
AU40532/97A AU4053297A (en) 1996-08-09 1997-08-08 Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
WO1998006759A1 true WO1998006759A1 (fr) 1998-02-19
WO1998006759A9 WO1998006759A9 (fr) 1998-06-25

Family

ID=26698395

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/013793 WO1998006759A1 (fr) 1996-08-09 1997-08-08 Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines

Country Status (1)

Country Link
WO (1) WO1998006759A1 (fr)

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001058912A1 (fr) * 2000-02-11 2001-08-16 The Dow Chemical Company Complexes ansa binucleaires a metal du groupe 4 contenant un pont bore ou aluminium
WO2001068719A1 (fr) * 2000-03-14 2001-09-20 Denki Kagaku Kogyo Kabushiki Kaisha Composant catalyseur a metal de transition pour la polymerisation, et procede de production de polymere a l'aide de ce composant
WO2002034759A1 (fr) * 2000-10-24 2002-05-02 Dow Global Technologies Inc. Complexes metalliques renfermant un groupe ylide ponte
WO2002076999A1 (fr) * 2001-03-23 2002-10-03 Bayer Aktiengesellschaft Catalyseurs presentant une interaction donneur-accepteur
WO2004094487A1 (fr) 2003-03-21 2004-11-04 Dow Global Technologies, Inc. Procede de polymerisation d'olefines avec controle de la morphologie
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 (fr) 2005-12-30 2007-07-04 Borealis Technology Oy Catalyseur de polymérisation à surface modifiée pour réduire la formation de gels dans des films
US7456244B2 (en) 2006-05-23 2008-11-25 Dow Global Technologies High-density polyethylene compositions and method of making the same
WO2010071798A1 (fr) 2008-12-18 2010-06-24 Univation Technologies, Llc Procédé de traitement d'un lit d'ensemencement pour une réaction de polymérisation
WO2010088265A1 (fr) 2009-01-30 2010-08-05 Dow Global Technologies Inc. Compositions de polyéthylène haute densité, leur procédé de fabrication, dispositifs de fermeture faits à partir de celles-ci et procédé de fabrication de tels dispositifs de fermeture
EP2218751A1 (fr) 2004-12-17 2010-08-18 Dow Global Technologies Inc. Compositions de polyéthylène modifié par rhéologie
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 (fr) 2012-12-28 2014-07-03 Univation Technologies, Llc Procédés consistant à intégrer la production d'aluminoxane dans la production de catalyseur
WO2014109832A1 (fr) 2013-01-14 2014-07-17 Univation Technologies, Llc Procédés de préparation de systèmes de catalyseurs ayant une productivité accrue
WO2016182920A1 (fr) 2015-05-08 2016-11-17 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2018063765A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2018063767A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Processus de polymérisation
WO2018063764A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2018118155A1 (fr) 2016-12-20 2018-06-28 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2019118073A1 (fr) 2017-12-13 2019-06-20 Exxonmobil Chemical Patents Inc. Procédés de désactivation pour composants actifs à partir d'un procédé de polymérisation de polyoléfine en phase gazeuse
WO2019173030A1 (fr) 2018-03-08 2019-09-12 Exxonmobil Chemical Patents Inc. Procédés de préparation et de surveillance d'un lit de germination pour le démarrage d'un réacteur de polymérisation
WO2019213227A1 (fr) 2018-05-02 2019-11-07 Exxonmobil Chemical Patents Inc. Procédés de mise à l'échelle superieure d'une installation pilote à une installation de production de plus grande taille
WO2019217173A1 (fr) 2018-05-02 2019-11-14 Exxonmobil Chemical Patents Inc. Procédés d'extrapolation d'une installation pilote à une installation de production plus grande
WO2020014138A1 (fr) 2018-07-09 2020-01-16 Exxonmobil Chemical Patents Inc. Films coulés de polyéthylène et procédés de fabrication de tels films coulés de polyéthylène
WO2020023207A1 (fr) 2018-07-26 2020-01-30 Exxonmobil Chemical Patents Inc. Films de mousse multicouches et leurs procédés de fabrication
WO2020102380A1 (fr) 2018-11-13 2020-05-22 Exxonmobil Chemical Patents Inc. Mélanges et films de polyéthylène
WO2020102385A1 (fr) 2018-11-13 2020-05-22 Exxonmobil Chemical Patents Inc. Films de polyéthylène
WO2020109870A2 (fr) 2018-06-28 2020-06-04 Exxonmobil Chemical Patents Inc. Compositions de polyéthylène, fils et câbles et procédés de réalisation de ceux-ci
WO2020163079A1 (fr) 2019-02-06 2020-08-13 Exxonmobil Chemical Patents Inc. Films et enveloppes de couche pour articles d'hygiène
WO2021126458A1 (fr) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Films constitués de mélanges de polyéthylène, destinés à améliorer les performances d'étanchéité et les propriétés mécaniques
WO2021183337A1 (fr) 2020-03-12 2021-09-16 Exxonmobil Chemical Patents Inc. Films constitués de mélanges de polyéthylène pour une rigidité à la flexion améliorée et une résistance à la déchirure en md élevée
US11447620B2 (en) 2007-05-02 2022-09-20 Dow Global Technologies Llc High-density polyethylene compositions, method of making the same, injection molded articles made therefrom, and method of making such articles
WO2022232760A1 (fr) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470993A (en) * 1993-06-24 1995-11-28 The Dow Chemical Company Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
US5486632A (en) * 1994-06-28 1996-01-23 The Dow Chemical Company Group 4 metal diene complexes and addition polymerization catalysts therefrom

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5470993A (en) * 1993-06-24 1995-11-28 The Dow Chemical Company Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
US5486632A (en) * 1994-06-28 1996-01-23 The Dow Chemical Company Group 4 metal diene complexes and addition polymerization catalysts therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0920455A4 *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001058912A1 (fr) * 2000-02-11 2001-08-16 The Dow Chemical Company Complexes ansa binucleaires a metal du groupe 4 contenant un pont bore ou aluminium
WO2001068719A1 (fr) * 2000-03-14 2001-09-20 Denki Kagaku Kogyo Kabushiki Kaisha Composant catalyseur a metal de transition pour la polymerisation, et procede de production de polymere a l'aide de ce composant
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 (ja) * 2000-03-14 2011-11-24 電気化学工業株式会社 重合用遷移金属触媒成分、それを用いた重合体の製造方法
WO2002034759A1 (fr) * 2000-10-24 2002-05-02 Dow Global Technologies Inc. Complexes metalliques renfermant un groupe ylide ponte
WO2002076999A1 (fr) * 2001-03-23 2002-10-03 Bayer Aktiengesellschaft Catalyseurs presentant une interaction donneur-accepteur
US6657027B2 (en) 2001-03-23 2003-12-02 Bayer Aktiengesellschaft Catalysts with a donor-acceptor interaction
WO2004094487A1 (fr) 2003-03-21 2004-11-04 Dow Global Technologies, Inc. Procede de polymerisation d'olefines avec controle de la morphologie
EP2218751A1 (fr) 2004-12-17 2010-08-18 Dow Global Technologies Inc. Compositions de polyéthylène modifié par rhéologie
EP1803747A1 (fr) 2005-12-30 2007-07-04 Borealis Technology Oy Catalyseur de polymérisation à surface modifiée pour réduire la formation de gels dans des 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
US7560524B2 (en) 2006-05-23 2009-07-14 Dow Global Technologies, Inc. High-density polyethylene compositions and method of making the same
US7456244B2 (en) 2006-05-23 2008-11-25 Dow Global Technologies High-density polyethylene compositions and method of making the same
US11447620B2 (en) 2007-05-02 2022-09-20 Dow Global Technologies Llc High-density polyethylene compositions, method of making the same, injection molded articles made therefrom, and method of making such articles
US7981517B2 (en) 2007-08-28 2011-07-19 Dow Global Technologies Inc. Bituminous compositions and methods of making and using same
WO2010071798A1 (fr) 2008-12-18 2010-06-24 Univation Technologies, Llc Procédé de traitement d'un lit d'ensemencement pour une réaction de polymérisation
US9056970B2 (en) 2009-01-30 2015-06-16 Dow Global Technologies Llc High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices
WO2010088265A1 (fr) 2009-01-30 2010-08-05 Dow Global Technologies Inc. Compositions de polyéthylène haute densité, leur procédé de fabrication, dispositifs de fermeture faits à partir de celles-ci et procédé de fabrication de tels dispositifs de fermeture
WO2014105614A1 (fr) 2012-12-28 2014-07-03 Univation Technologies, Llc Procédés consistant à intégrer la production d'aluminoxane dans la production de catalyseur
WO2014109832A1 (fr) 2013-01-14 2014-07-17 Univation Technologies, Llc Procédés de préparation de systèmes de catalyseurs ayant une productivité accrue
WO2016182920A1 (fr) 2015-05-08 2016-11-17 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2018063765A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2018063767A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Processus de polymérisation
WO2018063764A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2018118155A1 (fr) 2016-12-20 2018-06-28 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
WO2019118073A1 (fr) 2017-12-13 2019-06-20 Exxonmobil Chemical Patents Inc. Procédés de désactivation pour composants actifs à partir d'un procédé de polymérisation de polyoléfine en phase gazeuse
WO2019173030A1 (fr) 2018-03-08 2019-09-12 Exxonmobil Chemical Patents Inc. Procédés de préparation et de surveillance d'un lit de germination pour le démarrage d'un réacteur de polymérisation
WO2019217173A1 (fr) 2018-05-02 2019-11-14 Exxonmobil Chemical Patents Inc. Procédés d'extrapolation d'une installation pilote à une installation de production plus grande
WO2019213227A1 (fr) 2018-05-02 2019-11-07 Exxonmobil Chemical Patents Inc. Procédés de mise à l'échelle superieure d'une installation pilote à une installation de production de plus grande taille
WO2020109870A2 (fr) 2018-06-28 2020-06-04 Exxonmobil Chemical Patents Inc. Compositions de polyéthylène, fils et câbles et procédés de réalisation de ceux-ci
WO2020014138A1 (fr) 2018-07-09 2020-01-16 Exxonmobil Chemical Patents Inc. Films coulés de polyéthylène et procédés de fabrication de tels films coulés de polyéthylène
WO2020023207A1 (fr) 2018-07-26 2020-01-30 Exxonmobil Chemical Patents Inc. Films de mousse multicouches et leurs procédés de fabrication
WO2020102380A1 (fr) 2018-11-13 2020-05-22 Exxonmobil Chemical Patents Inc. Mélanges et films de polyéthylène
WO2020102385A1 (fr) 2018-11-13 2020-05-22 Exxonmobil Chemical Patents Inc. Films de polyéthylène
WO2020163079A1 (fr) 2019-02-06 2020-08-13 Exxonmobil Chemical Patents Inc. Films et enveloppes de couche pour articles d'hygiène
WO2021126458A1 (fr) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Films constitués de mélanges de polyéthylène, destinés à améliorer les performances d'étanchéité et les propriétés mécaniques
WO2021183337A1 (fr) 2020-03-12 2021-09-16 Exxonmobil Chemical Patents Inc. Films constitués de mélanges de polyéthylène pour une rigidité à la flexion améliorée et une résistance à la déchirure en md élevée
WO2022232760A1 (fr) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation

Similar Documents

Publication Publication Date Title
WO1998006759A1 (fr) Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines
WO1998006759A9 (fr) Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines
Pédeutour et al. Reactivity of metallocene catalysts for olefin polymerization: influence of activator nature and structure
CA2027144C (fr) Methode et catalyseur pour la preparation de polyolefines syndiotactiques
US6051667A (en) Olefin polymerization using a catalyst having a bridged cyclopentadienyl-phosphole ligand
JP3293927B2 (ja) α‐オレフィン重合用触媒成分およびそれを用いたα‐オレフィン重合体の製造法
EP0573403A2 (fr) Catalyseurs métallocènes cationiques à base d'aluminium triphénylcarbénium
KR20010024020A (ko) 2-금속 착체 및 이로부터 제조된 중합 촉매
US5962714A (en) Monocyclopentadienyl transition metal catalyst and olefin polymerization process
JP3779759B2 (ja) メタロセン化合物及び触媒成分としてのその使用
US5939503A (en) Group IV zwitterion ansa metallocene (ZAM) catalysts for α-olefin polymerization
CN101258171B (zh) 用于制备乙烯均聚物或乙烯与α-烯烃的共聚物的均相催化剂体系
US6100414A (en) Cyclopentadienyl transition metal compounds useful as polymerization catalysts
Lancaster et al. Anionic a nsa-Zirconocenes with Pentafluorophenyl-Substituted Borato Bridges
WO1995010546A1 (fr) Procede pour la polymerisation d'une olefine en presence d'un systeme de catalyseur comprenant un metallocene d'halogene
JP2004530653A (ja) 非メタロセン、その製造方法およびオレフィンの重合での使用
JPH0748408A (ja) オレフィンの重合方法
JPH05230133A (ja) オレフィンの重合触媒及びそれを用いたポリオレフィンの製造方法
JPH05230135A (ja) 分子量分布の広いポリオレフィンの製造方法
US6753436B2 (en) Olefin polymerization catalysts
US6271322B1 (en) Monocyclopentadienyl transition metal catalyst and olefin polymerization process
US6437187B1 (en) Compounds having an ionic structure used as constituent of an olefin polymerization catalyst
WO1997023493A1 (fr) Compose d'un metal de transition, son procede de preparation et son utilisation comme constituant catalyseur
JPH07173208A (ja) 新規メタロセン化合物及びそれを用いたオレフィンの重合方法
JP3427488B2 (ja) 新規有機遷移金属化合物およびそれを用いたポリオレフィンの製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT. BUL. 07/98, UNDER INID (30) "PRIORITY DATA", REPLACE "NOT FURNISHED" BY "08/907395"

121 Ep: the epo has been informed by wipo that ep was designated in this application
COP Corrected version of pamphlet

Free format text: PAGES 8 AND 9, DESCRIPTION, REPLACED BY NEW PAGES 8 AND 9; PAGES 1/2-2/2, DRAWINGS, REPLACED BY NEWPAGES 1/2-2/2; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

WWE Wipo information: entry into national phase

Ref document number: 1997938137

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998509828

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1997938137

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWG Wipo information: grant in national office

Ref document number: 1997938137

Country of ref document: EP