CA2736014A1 - Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength - Google Patents

Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength Download PDF

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Publication number
CA2736014A1
CA2736014A1 CA2736014A CA2736014A CA2736014A1 CA 2736014 A1 CA2736014 A1 CA 2736014A1 CA 2736014 A CA2736014 A CA 2736014A CA 2736014 A CA2736014 A CA 2736014A CA 2736014 A1 CA2736014 A1 CA 2736014A1
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Prior art keywords
homopolymer
copolymer
further characterized
blown film
article
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Granted
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CA2736014A
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French (fr)
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CA2736014C (en
Inventor
Michael D. Jensen
Joel L. Martin
Max P. Mcdaniel
Qing Yang
Matthew G. Thorn
Elizabeth A. Benham
Ted H. Cymbaluk
Ashish M. Sukhadia
Rajendra K. Krishnaswamy
Mark E. Kertok
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Chevron Phillips Chemical Co LP
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Chevron Phillips Chemical Co LP
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Expired - Fee Related legal-status Critical Current
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/07Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component 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
    • C08F4/65922Component 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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925Component 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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component 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
    • C08F4/65922Component 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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927Component 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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/941Synthetic resins or natural rubbers -- part of the class 520 series having the transition metal bonded directly to carbon
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

Abstract

This invention relates to catalyst compositions comprising a first metallocene compound, a second metallocene compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound. This invention also relates to methods to prepare and use the catalyst compositions and new polyolefins. The compositions and methods disclosed herein provide ethylene polymers and copolymers with lower MI, increased melt strength, and good MD tear properties.

Claims (21)

1. A homopolymer or copolymer of ethylene having a melt index (MI) from about 0.3 to about 2.0 dg/min, a high load melt index (HLMI) to melt index ratio (HLMI/MI) from about 16.5 to about 25, a polydispersity index (M w/M n) from about 2 to about 6, a CY-a parameter from about 0.45 to about 0.70, a MD Elmendorf tear resistance greater than about 150 g for a 1 mil blown film, a TD Elmendorf tear resistance greater than about 350 g for a 1 mil blown film, and a Dart impact strength greater than about 800 g for a 1 mil blown film.
2. The homopolymer or copolymer of claim 1, further characterized by a high load melt index (HLMI) from about 10 to about 30 dg/min.
3. The homopolymer or copolymer of claim 1, further characterized by a HLM/MI
ratio from about 17 to about 24.
4. The homopolymer or copolymer of claim 1, further characterized by a density from about 0.91 to about 0.94 g/cm3.
5. The homopolymer or copolymer of claim 1, further characterized by a film haze less than about 25% for a 1 mil blown film.
6. The homopolymer or copolymer of claim 1, further characterized by a CY-a parameter from about 0.50 to about 0.65.
7. The homopolymer or copolymer of claim 1, further characterized by a Spencer impact strength greater than about 0.7 J for a 1 mil blown film.
8. An article comprising the homopolymer or copolymer of claim 1.
9. The article of claim 8, wherein the article is a household container, an utensil, a film product, a drum, a fuel tank, a pipe, a geomembrane, or a liner.
10. The article of claim 8, wherein the article is a blown film product.
11. The homopolymer or copolymer of claim 1, further characterized by a Dart impact strength greater than about 1200 g for a 1 mil blown film.
12. A homopolymer or copolymer of ethylene having a melt index (MI) from about 0.3 to about 2.0 dg/min, a high load melt index (HLMI) to melt index ratio (HLMI/MI) from about 16.5 to about 25, a polydispersity index (M w/M n) from about 2.6 to about 4, a CY-a parameter from about 0.45 to about 0.70, a MD Elmendorf tear resistance greater than about 150 g for a 1 mil blown film, a TD Elmendorf tear resistance greater than about 350 g for a 1 mil blown film, and a Dart impact strength greater than about 600 g for a 1 mil blown film.
13. The homopolymer or copolymer of claim 12, further characterized by a high load melt index (HLMI) from about 10 to about 30 dg/min.
14. The homopolymer or copolymer of claim 12, further characterized by a HLMI/MI
ratio from about 17 to about 24.
15. The homopolymer or copolymer of claim 12, further characterized by a density from about 0.91 to about 0.94 g/cm3.
16. The homopolymer or copolymer of claim 12, further characterized by a film haze less than about 25% for a 1 mil blown film.
17. The homopolymer or copolymer of claim 12, further characterized by a CY-a parameter from about 0.50 to about 0.65.
18. The homopolymer or copolymer of claim 12, further characterized by a Spencer impact strength greater than about 0.7 J for a 1 mil blown film.
19. An article comprising the homopolymer or copolymer of claim 12.
20. The article of claim 19, wherein the article is a household container, an utensil, a film product, a drum, a fuel tank, a pipe, a geomembrane, or a liner.
21. The article of claim 19, wherein the article is a blown film product.
CA2736014A 2004-01-21 2005-01-20 Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength Expired - Fee Related CA2736014C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/762,056 2004-01-21
US10/762,056 US7119153B2 (en) 2004-01-21 2004-01-21 Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
CA2553993A CA2553993C (en) 2004-01-21 2005-01-20 Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CA2553993A Division CA2553993C (en) 2004-01-21 2005-01-20 Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength

Publications (2)

Publication Number Publication Date
CA2736014A1 true CA2736014A1 (en) 2005-08-04
CA2736014C CA2736014C (en) 2012-11-27

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CA2553993A Expired - Fee Related CA2553993C (en) 2004-01-21 2005-01-20 Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength
CA2736014A Expired - Fee Related CA2736014C (en) 2004-01-21 2005-01-20 Dual metallocene catalyst for producing film resins with good machine direction (md) elmendorf tear strength

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US (2) US7119153B2 (en)
EP (1) EP1706437B1 (en)
JP (3) JP2007518871A (en)
CN (2) CN101475654B (en)
AU (2) AU2005206563B2 (en)
BR (1) BRPI0507047A (en)
CA (2) CA2553993C (en)
EG (1) EG26673A (en)
ES (1) ES2563165T3 (en)
MX (1) MXPA06008322A (en)
RU (1) RU2382793C2 (en)
SG (1) SG134326A1 (en)
WO (1) WO2005070977A1 (en)

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