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DE420436T1 - Katalysatoren zur Polymerisation von Olefinen. - Google Patents

Katalysatoren zur Polymerisation von Olefinen.

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Publication number
DE420436T1
DE420436T1 DE0420436T DE90309899T DE420436T1 DE 420436 T1 DE420436 T1 DE 420436T1 DE 0420436 T DE0420436 T DE 0420436T DE 90309899 T DE90309899 T DE 90309899T DE 420436 T1 DE420436 T1 DE 420436T1
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group
hydrocarbon
substituted
ligand
radicals
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DE0420436T
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Inventor
Jo Ann Marie Houston Texas 77058 Canich
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of DE420436T1 publication Critical patent/DE420436T1/de
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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
    • 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
    • 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
    • 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
    • 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
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT 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
    • C08F4/65908—Component covered by group C08F4/64 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
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)

Claims (17)

EP 90309899.4 , 0420 435 Patentansprüche:
1. Metallocenverbindung, die einen einzigen mono- oder polycyclischen Cyclopentadienylliganden und einen Heteroatomliganden mit einem Gruppe-V-A- oder -VI-A-Element enthält, die an ein Gruppe-IV-B-Übergangsmetallatom gebunden sind.
2. Verbindung nach Anspruch 1, in der das Heteroatom Stickstoff, Phosphor, Sauerstoff oder Schwefel ist.
3. Verbindung nach Anspruch 1 oder Anspruch 2, in der der cyclische Ligand substituiert oder unsubstituiert ist.
4. Verbindung nach einem der vorhergehenden Ansprüche, in der das Übergangsmetallatom Zirconium oder Hafnium ist.
5. Verbindung nach einem der vorhergehenden Ansprüche, in der zwei anionische Liganden an das Übergangsmetallatom gebunden sind, wobei die anionischen Liganden entweder einwertig oder zweiwertig sind, wobei in diesem Fall ein solcher Ligand an ein weiteres Übergangsmetallatom mit cyclischen und Heteroatomliganden gebunden sein kann.
6. Verbindung mit der allgemeinen Formel
By m^ Q
(JR' )
2-1-y
oder
0420 435
/ (JR'
z- -y-xRx) Q'
. I/ (JR1
/&khgr; -l-y» /
B
y /K M1
y \ \ \ i \ V /
in der M Zr, Hf oder Ti ist;
(C5H5-7.^) ein Cyclopentadienylring ist, der mit null bis fünf Gruppen R substituiert ist, "x" 1, 2, 3, 4 oder 5 ist und den Substitutionsgrad bedeutet und jedes R unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1- bis C2o-Kohlenwasserstoffresten, substituierten C1- bis C20-KOhlenwasserstof fresten, in denen ein oder mehrere Wasserstof fatome durch ein Halogenatom ersetzt sind, C1- bis C20-kohlenwasserstoffsubstituierten Metalloidresten, in denen das Metalloid ausgewählt ist aus der Gruppe IV A des Periodensystems der Elemente, und Halogenresten ist, oder (C5H5-7^Rx) ein Cyclopentadienylring ist, in welchem zwei benachbarte R-Gruppen unter Bildung eines C4- bis C20-Rings verbunden sind, um einen gesättigten oder ungesättigten polycyclischen Cyclopentadienylliganden zu ergeben;
(JR'z-i.7) ein Heteroatomligand ist, in dem J ein Element mit einer Koordinat ions zahl von drei aus der Gruppe V A oder ein Element mit einer Koordinationszahl von zwei aus der Gruppe VI A des Periodensystems der Elemente ist, jedes R' unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1-bis C20-Kohlenwasserstoffresten und substituierten C1- bis C20-Kohlenwasserstoffresten, in denen ein oder mehrere Wasserstof fatome durch ein Halogenatom ersetzt worden sind, und "z" die Koordinationszahl des Elementes J ist;
jedes Q unabhängig ein beliebiger einwertiger anionischer Ligand ist oder zwei Q ein zweiwertiges anionisches Chelierungsmittel sind,
- 3 - 0420 435
"y" O oder 1 ist, wenn w größer als 0 ist; y gleich 1 ist, wenn w 0 ist; wenn "y" 1 ist, B eine kovalente Brückengruppe ist, die ein Gruppe IV A oder V A Element enthält; und L eine Lewisbase ist, wobei
tet.
7. Verbindung mit der allgemeinen Formel
(C.H, R„)
-Q
(JR' „)
z-2
in der M Zr, Hf oder Ti ist;
(C5H4.^) ein Cyclopentadienylring ist, der mit null bis vier Gruppen R substituiert ist, "x" 1, 2, 3 oder 4 ist und den Substitutionsgrad bedeutet und jede Substituentengruppe R unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1- bis C20-Kohlenwasserstoffresten, substituierten C1-bis C2o-Kohlenwasserstoffresten, in denen ein oder mehrere Wasserstoffatome durch ein Halogenatom ersetzt sind, C1- bis C20-kohlenwasserstoff substituierten Metalloidresten, in denen das Metalloid ausgewählt ist aus der Gruppe IV A des Periodensystems der Elemente, und Halogenresten ist, oder (C5H4^Rx) ein Cyclopentadienylring ist, in welchem zwei benachbarte R-Gruppen unter Bildung eines C4- bis C20-Rings verbunden sind, um einen gesättigten oder ungesättigten polycyclischen Cyclopentadienylliganden zu ergeben;
-A-
0420 435
(JR'Z_2) ein Heteroatom!.igand ist, in dem J ein Element mit einer Koordinations zahl von drei aus der Gruppe V A oder ein Element mit einer Koordinationszahl von zwei aus der Gruppe VI A des Periodensystems der Elemente ist, jedes R' unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1-bis C2o-Kohlenwasserstoffresten und substituierten C1- bis C2o-Kohlenwasserstoffresten, in denen ein oder mehrere Wasserstoffatome durch ein Halogenatom ersetzt worden sind, und "z" die Koordinationszahl des Elementes J ist; jedes Q unabhängig ein beliebiger einwertiger anionischer Ligand ist oder zwei Q ein zweiwertiger anionischer chelierender Ligand sind,
B eine kovalente Brückengruppe ist, die ein Gruppe-IV-A- oder -V-A-Element enthält, und
L eine Lewisbase ist, wobei "w" eine Zahl von 0 bis 3 bedeutet.
8. Verbindung nach Anspruch 6 oder 7, in der Q ein Hydrid, Halogen oder ein von einer cyclischen Cyclopentadienylgruppe verschiedener Kohlenwasserstoffrest ist.
9. Verbindung nach Anspruch 8, in der Q substituierter oder unsubstituierter C1- bis C^-Kohlenwasserstoff, Alkoxid, Aryloxid, Amid, Arylamid, Phosphid oder Arylphosphid ist, mit der Maßgabe, daß wenn irgendein Q ein solches ist, sich Q von (C5H4-3-Rx) unterscheidet, oder beide zusammen ein Alkyliden oder cyclometallierter Kohlenwasserstoff sind.
10. Katalysatorsystem zur Olefinpolymerisation, das (A) eine Verbindung nach einem der vorhergehenden Ansprüche und (B) ein Alumoxan oder (C) ein Reaktionsprodukt aus einer solchen Verbindung, einem Aluminiumalkyl und Wasser umfaßt.
11. Katalysatorsystem nach Anspruch 7, bei dem das Molverhältnis von A1:M 10:1 bis 20 000:1 beträgt.
0420 435
12. Verfahren zur Herstellung eines Olefinpolymers unter Verwendung eines Katalysatorsystems gemäß Anspruch 10 oder 11.
13. Verfahren nach Anspruch 12, bei dem die Metallocenverbindung, das Alumoxan oder das Aluminiumalkyl und Wasser vor der Polymerisation teilweise oder vollständig umgesetzt werden.
14. Verfahren zur Herstellung einer Verbindung nach einem der Ansprüche 6 bis 9, bei dem ein Gruppe-IV-B-Übergangsmetallhalogenid mit einem Salz umgesetzt wird, das ein Anion mit der Formel [ (C5H4.^)-B-(JR'z_2) ]2~ und entweder zwei Kationen aus der Gruppe I A des Periodensystems der Elemente oder ein Kation aus der Gruppe II A des Periodensystems der Elemente enthält.
15. Verfahren nach Anspruch 14/ bei dem das Kation Lithium ist.
16. Verfahren nach Anspruch 14 oder Anspruch 15, bei dem das Gruppe-IV-B-Metallhalogenid Zirconium(IV)chlorid oder Hafnium (IV)Chlorid ist.
17. Verfahren nach einem der vorhergehenden Ansprüche 14 bis 16, bei dem Q unabhängig Halogen, Hydrid oder substituierter oder unsubstituierte C1- bis C20-Kohlenwasserstoff, Alkoxid, Aryloxid, Amid, Arylamid, Phosphid oder Arylphosphid ist, mit der Maßgabe, daß wenn irgendein Q Kohlenwasserstoff ist, dieses Q sich von (C5H4-1Rx) unterscheidet, oder beide Q zusammen ein Alkyliden oder cyclometallierter Kohlenwasserstoff sind.
DE0420436T 1989-09-13 1990-09-10 Katalysatoren zur Polymerisation von Olefinen. Pending DE420436T1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40694589A 1989-09-13 1989-09-13
US07/533,245 US5055438A (en) 1989-09-13 1990-06-04 Olefin polymerization catalysts

Publications (1)

Publication Number Publication Date
DE420436T1 true DE420436T1 (de) 1996-02-15

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Application Number Title Priority Date Filing Date
DE0420436T Pending DE420436T1 (de) 1989-09-13 1990-09-10 Katalysatoren zur Polymerisation von Olefinen.
DE0662484T Pending DE662484T1 (de) 1989-09-13 1990-09-10 Katalysatore für Olefinpolymerisation.
DE69028057T Expired - Lifetime DE69028057T3 (de) 1989-09-13 1990-09-10 Katalysatoren zur Polymerisation von Olefinen
DE69030442T Revoked DE69030442T2 (de) 1989-09-13 1990-09-13 Katalysatoren zur polymerisation von olefinen

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DE0662484T Pending DE662484T1 (de) 1989-09-13 1990-09-10 Katalysatore für Olefinpolymerisation.
DE69028057T Expired - Lifetime DE69028057T3 (de) 1989-09-13 1990-09-10 Katalysatoren zur Polymerisation von Olefinen
DE69030442T Revoked DE69030442T2 (de) 1989-09-13 1990-09-13 Katalysatoren zur polymerisation von olefinen

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US (4) US5055438A (de)
EP (5) EP0662484A3 (de)
JP (2) JP2994746B2 (de)
KR (2) KR100190735B1 (de)
AR (1) AR244355A1 (de)
AT (2) ATE141275T1 (de)
AU (1) AU6248390A (de)
BR (2) BR9004537A (de)
CA (2) CA2024899C (de)
DD (1) DD300233A5 (de)
DE (4) DE420436T1 (de)
DK (2) DK0420436T4 (de)
ES (2) ES2091801T5 (de)
FI (2) FI109705B (de)
GR (2) GR3021539T3 (de)
HU (1) HU214667B (de)
IL (1) IL95549A0 (de)
NO (2) NO178891C (de)
NZ (1) NZ235095A (de)
PT (1) PT95272B (de)
WO (1) WO1991004257A1 (de)

Families Citing this family (709)

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US5055438A (en) * 1989-09-13 1991-10-08 Exxon Chemical Patents, Inc. Olefin polymerization catalysts
USRE37788E1 (en) * 1987-01-30 2002-07-09 Exxon Chemical Patents, Inc. Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5621126A (en) 1987-01-30 1997-04-15 Exxon Chemical Patents Inc. Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5264405A (en) * 1989-09-13 1993-11-23 Exxon Chemical Patents Inc. Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts
US5830087A (en) * 1995-06-26 1998-11-03 Lisco, Inc. Multi-layer golf ball
GB8914703D0 (en) * 1989-06-27 1989-08-16 Dow Europ Sa Bioriented film
NZ235032A (en) * 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
US6686488B2 (en) 1989-08-31 2004-02-03 The Dow Chemical Company Constrained geometry addition polymerization catalysts
US6025448A (en) 1989-08-31 2000-02-15 The Dow Chemical Company Gas phase polymerization of olefins
US5763547A (en) * 1992-10-02 1998-06-09 The Dow Chemical Company Supported catalyst complexes for olefin in polymerization
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