WO2005104940A2 - Heterophasic copolymer and metallocene catalyst system - Google Patents

Heterophasic copolymer and metallocene catalyst system Download PDF

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Publication number
WO2005104940A2
WO2005104940A2 PCT/US2005/011605 US2005011605W WO2005104940A2 WO 2005104940 A2 WO2005104940 A2 WO 2005104940A2 US 2005011605 W US2005011605 W US 2005011605W WO 2005104940 A2 WO2005104940 A2 WO 2005104940A2
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WO
WIPO (PCT)
Prior art keywords
heterophasic polymer
metallocene catalyst
catalyst system
reaction zone
support
Prior art date
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Ceased
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PCT/US2005/011605
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English (en)
French (fr)
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WO2005104940A3 (en
Inventor
Jun Tian
William J. Gauthier
Kenneth Paul Blackmon
David J. Rauscher
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Fina Technology Inc
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Fina Technology Inc
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Publication date
Application filed by Fina Technology Inc filed Critical Fina Technology Inc
Priority to CA002553496A priority Critical patent/CA2553496A1/en
Priority to JP2007509494A priority patent/JP2007533824A/ja
Priority to CN2005800115432A priority patent/CN1972994B/zh
Priority to EP05732650A priority patent/EP1737909A4/en
Publication of WO2005104940A2 publication Critical patent/WO2005104940A2/en
Anticipated expiration legal-status Critical
Publication of WO2005104940A3 publication Critical patent/WO2005104940A3/en
Ceased legal-status Critical Current

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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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • 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
    • C08F4/65912—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
    • C08F4/6592—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
    • C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • R 2 is a structural bridge between the two (C 5 - n (R 1 )n) rings imparting stereo-rigidity to the metallocene with the two (C5- n (R 1 ) n ) rings being in a rac or meso configuration relative to Me.
  • R 2 is selected from the group consisting of an alkylene radical having 1-20 carbon atoms, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrocarbyl radical.
  • the homopolymer matrix produced in the first reaction step may be a homopolymer of, for example propylene
  • small amounts of a co- monomer may be incorporated into the first reaction zone to obtain particular properties in the resulting first reaction zone polymer matrix. If co-monomer is added, the amount generally may be less than ten weight percent (10 wt%) of the primary monomer. However, such co-monomer, if present, will be present in an amount of less than about one weight percent (1 wt%).
  • the catalytic activity (CA) of the MCS for the production of the homopolymer is measured following the methodology described in U.S. Patent Applications 09/782,752 and 09/782,753 to Gauthier et al. Briefly, unless otherwise indicated, the polymerization is carried out in bulk phase in a conventional 4 L Autoclave Zipperclave reactor chamber, in the presence of about 24 millimoles H2, about 1300 g propylene, and about 90 mg of TEA, at about 67°C for one hour. For runs (1) and (2) using MS-1733, about 15 mg and about 20 mg of MCS are used. All measurements conducted using G-948 and P-10 are conducted under the same conditions, but using about 25 mg of MCS.
  • the preparation of the homopolymer of the present invention is repeated substantially as described hereinabove, with the following exceptions.
  • the first reaction phase is carried out in bulk phase at about 70°C for about 20 to 45 minutes in the presence of about 0.07 mol% H 2 .
  • the apparatus used is a conical funnel 230 mm in height with a top opening of 127 mm and hnttnm nnonin ⁇ r»f A mm T ⁇ hnttnm ⁇ -vf t ⁇ f ⁇ ⁇ nn ⁇ _-l io CQ IQ on i in ⁇ ln ⁇ H Konrl and iM&Im ⁇ &' ⁇ . ⁇ ⁇ ed to the funnel gently through the top opening.
  • the amount of polymer used ranged from 36 to 160 grams. Where possible, 160 grams are used.
  • the bottom of the funnel is opened and a timer started at the same instant.
  • the ethylene wt% is thought to represent the ethylene content of the rubber fraction because there is substantially no ethylene present in the homopolymer, i.e., less than about 0.1 %.
  • 100 g of ICP prepared using an MCS supported by MS-1733 would contain about 12.8 g of rubber, about 4 g of which corresponds to ethylene.
  • the ethylene content of the rubber fraction equals about 33%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Graft Or Block Polymers (AREA)
PCT/US2005/011605 2004-04-20 2005-04-07 Heterophasic copolymer and metallocene catalyst system Ceased WO2005104940A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002553496A CA2553496A1 (en) 2004-04-20 2005-04-07 Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system
JP2007509494A JP2007533824A (ja) 2004-04-20 2005-04-07 ヘテロ相コポリマ−及びメタロセン触媒系並びにこのメタロセン触媒系を用いる該ヘテロ相コポリマ−の製造法
CN2005800115432A CN1972994B (zh) 2004-04-20 2005-04-07 多相共聚物和茂金属催化剂体系和使用该体系制备多相共聚物的方法
EP05732650A EP1737909A4 (en) 2004-04-20 2005-04-07 HETEROPHASIC COPOLYMER AND METALLOCENE CATALYST SYSTEM AND METHOD FOR PRODUCING THE HETEROPHASIC COPOLYMER USING THE METALOCENE CATALYST SYSTEM

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/827,959 2004-04-20
US10/827,959 US20050234198A1 (en) 2004-04-20 2004-04-20 Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system

Publications (2)

Publication Number Publication Date
WO2005104940A2 true WO2005104940A2 (en) 2005-11-10
WO2005104940A3 WO2005104940A3 (en) 2006-11-09

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Application Number Title Priority Date Filing Date
PCT/US2005/011605 Ceased WO2005104940A2 (en) 2004-04-20 2005-04-07 Heterophasic copolymer and metallocene catalyst system

Country Status (8)

Country Link
US (1) US20050234198A1 (enExample)
EP (1) EP1737909A4 (enExample)
JP (1) JP2007533824A (enExample)
KR (1) KR20070004604A (enExample)
CN (1) CN1972994B (enExample)
CA (1) CA2553496A1 (enExample)
TW (1) TW200604230A (enExample)
WO (1) WO2005104940A2 (enExample)

Cited By (4)

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WO2009077032A1 (en) * 2007-12-17 2009-06-25 Borealis Technology Oy Heterophasic polypropylene with high flowability and excellent low temperature impact properties
EP2426171A1 (en) 2010-08-30 2012-03-07 Borealis AG Heterophasic polypropylene with high flowability and enhanced mechanical properties
WO2025157819A1 (en) * 2024-01-22 2025-07-31 Sabic Global Technologies B.V. Catalyst system for multi-stage olefin polymerisation

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US20080287619A1 (en) * 2007-05-18 2008-11-20 William Gauthier Supported metallocene catalysts
EP2141200A1 (en) * 2008-07-03 2010-01-06 Total Petrochemicals Research Feluy Heterophasic propylene copolymer with improved properties for injection molding applications
EP2275476A1 (en) 2009-06-09 2011-01-19 Borealis AG Automotive material with excellent flow, high stiffness, excellent ductility and low CLTE
WO2016196339A2 (en) * 2015-06-05 2016-12-08 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
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EP1737909A4 (en) 2008-07-23
CN1972994B (zh) 2013-01-16
CN1972994A (zh) 2007-05-30
TW200604230A (en) 2006-02-01
WO2005104940A3 (en) 2006-11-09
JP2007533824A (ja) 2007-11-22
CA2553496A1 (en) 2005-11-10
US20050234198A1 (en) 2005-10-20
KR20070004604A (ko) 2007-01-09
EP1737909A2 (en) 2007-01-03

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