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Robust spray-dried ziegler-natta procatalyst and polymerization process employing same

Info

Publication number
CA2574364A1
CA2574364A1 CA 2574364 CA2574364A CA2574364A1 CA 2574364 A1 CA2574364 A1 CA 2574364A1 CA 2574364 CA2574364 CA 2574364 CA 2574364 A CA2574364 A CA 2574364A CA 2574364 A1 CA2574364 A1 CA 2574364A1
Authority
CA
Grant status
Application
Patent type
Prior art keywords
composition
particles
procatalyst
size
compound
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CA 2574364
Other languages
French (fr)
Other versions
CA2574364C (en )
Inventor
Robert J. Jorgensen
Michael A. Kinnan
Michael D. Turner
Stephanie M. Whited
Laszlo L. Ban
Burkhard Eric Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Chemicals and Plastics Technology LLC
Original Assignee
Robert J. Jorgensen
Michael A. Kinnan
Michael D. Turner
Stephanie M. Whited
Laszlo L. Ban
Burkhard Eric Wagner
Union Carbide Chemicals & Plastics Technology Corporation
Union Carbide Chemicals & Plastics Technology Llc
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

Links

Classifications

    • 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
    • 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
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene

Abstract

A Ziegler-Natta procatalyst composition in the form of solid particles and comprising magnesium, halide and transition metal moieties, said particles having an average size (D50) of from 10 to 70 ~m, characterized in that at least 5 percent of the particles have internal void volume substantially or fully enclosed by a monolithic surface layer (shell), said layer being characterized by an average shell thickness/ particle size ratio (Thickness Ratio) determined by SEM techniques for particles having particle size greater than 30 ~m of greater than 0.2.

Claims (15)

1. A Ziegler-Natta procatalyst composition in the form of solid particles and comprising magnesium, halide and transition metal moieties, said particles having an average size (D50) of from 10 to 70 µm, characterized in that at least 5 percent of the particles have internal void volume substantially or fully enclosed by a monolithic surface layer (shell), said layer being characterized by an average shell thickness/ particle size ratio (Thickness Ratio) determined by SEM
techniques for particles having particle size greater than 30 µm of greater than 0.2.
2. The composition according to claim 1 wherein the average particle size is from 20 to 35 µm.
3. The composition according to claim 1 wherein at least 25 percent of the particles have a Thickness Ratio of greater than 0.2.
4. The composition according to claim 2 wherein at least 25 percent of the particles have a Thickness Ratio of greater than 0.25.
5. The composition according to claim 1 wherein the procatalyst composition corresponds to the formula: [Mg(R1OH)r]d Ti(OR e)e X f[ED]q,, wherein R1OH
comprises a monofunctional, linear or branched alcohol having between one and 25 carbon atoms; R e is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR' wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR
e group is the same or different; X is independently R', chlorine, bromine or iodine; d is 0.5 to 5; e is 0-12; and f is 1-10, ED is an electron donor; q ranges from 0 to 50; and r is 0, 1, or 2.
6. The composition of claim 5 which is prepared by the reaction of magnesium dichloride with a titanium compound in the presence of an alcohol.
7. The composition of claim 6 wherein the transition metal compound is a titanium halide or a titanium haloalcoholate having 1 to 8 carbon atoms per alcoholate group.
8. The composition of claim 6 wherein the titanium compound is TiCl3.
9. The composition of claim 1 additionally comprising a filler.
10. The composition of claim 9 wherein the filler is fumed silica present in the solid particles in an amount of at least 15 percent based on total composition weight.
11. A method for making the procatalyst composition of claim 1, the steps of the method comprising: a) providing a liquid composition comprising i) a magnesium halide compound, ii) a solvent or diluent, iii) a transition metal compound wherein the transition metal is selected from the metals of Groups 3-10 and Lanthanides of the Periodic Table of the Elements, iv) optionally an internal electron donor, and v) further optionally a filler; b) spray-drying the composition to form a spray-dried particle; and c) collecting the resulting solid particles, characterized in that the magnesium halide compound forms a substantially saturated solution in the solvent or diluent.
12. The method of claim 11 wherein the solvent or diluent is tetrahydrofuran.
13. The method of claim 11 wherein the magnesium halide compound is present in an amount that is at least 90 percent of the saturation concentration in the solvent or diluent.
14. A process for making a polymer comprising contacting at least one olefin monomer with a procatalyst according to any one of claims 1-10 or with a procatalyst made by the method of any one of claims 11-13, and a cocatalyst under olefin polymerization conditions to form a polymer product..
15. A process according to claim 14 wherein ethylene is homopolymerized or copolymerized with one or more .alpha.-olefins.
CA 2574364 2004-08-09 2005-06-24 Robust spray-dried ziegler-natta procatalyst and polymerization process employing same Expired - Fee Related CA2574364C (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US60008204 true 2004-08-09 2004-08-09
US60/600,082 2004-08-09
PCT/US2005/022492 WO2006023057A1 (en) 2004-08-09 2005-06-24 Robust spray-dried ziegler-natta procatalyst and polymerization process employing same

Publications (2)

Publication Number Publication Date
CA2574364A1 true true CA2574364A1 (en) 2006-03-02
CA2574364C CA2574364C (en) 2012-11-27

Family

ID=35395595

Family Applications (2)

Application Number Title Priority Date Filing Date
CA 2574364 Expired - Fee Related CA2574364C (en) 2004-08-09 2005-06-24 Robust spray-dried ziegler-natta procatalyst and polymerization process employing same
CA 2576560 Abandoned CA2576560A1 (en) 2004-08-09 2005-08-09 Robust spray-dried ziegler-natta procatalyst and polymerization process employing same

Family Applications After (1)

Application Number Title Priority Date Filing Date
CA 2576560 Abandoned CA2576560A1 (en) 2004-08-09 2005-08-09 Robust spray-dried ziegler-natta procatalyst and polymerization process employing same

Country Status (9)

Country Link
US (2) US8173569B2 (en)
JP (1) JP5363728B2 (en)
KR (2) KR101200656B1 (en)
CN (3) CN102516423A (en)
CA (2) CA2574364C (en)
EP (2) EP1778744B1 (en)
ES (1) ES2535821T3 (en)
RU (2) RU2377256C2 (en)
WO (1) WO2006023057A1 (en)

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JP2008509276A (en) * 2004-08-09 2008-03-27 ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション Spray-dried rugged Ziegler-Natta procatalyst, and a polymerization method using the same
KR20090024671A (en) 2006-04-07 2009-03-09 다우 글로벌 테크놀로지스 인크. Polyolefin compositions, articles made therefrom and methods for preparing the same
EP2076565B1 (en) 2006-10-23 2010-06-02 Dow Global Technologies Inc. Polyethylene compositions, methods of making the same, and articles prepared therefrom
CN102030846B (en) 2009-09-29 2012-06-13 上海化工研究院 Catalyst capable of preparing polyethylene with high melt flow ratio and preparation method thereof
US20130075409A1 (en) 2010-04-14 2013-03-28 Mridula Kapur Fuel containers made from polyethylene compositions with improved creep resistance
CN104776687B (en) * 2014-09-05 2017-09-29 山东诚创医药技术开发有限公司 Colesevelam hydrochloride drying test of a polymer

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Also Published As

Publication number Publication date Type
CA2576560A1 (en) 2006-02-23 application
KR101200656B1 (en) 2012-11-12 grant
KR20070061522A (en) 2007-06-13 application
RU2007108543A (en) 2008-09-20 application
US20120178888A1 (en) 2012-07-12 application
EP1778744A1 (en) 2007-05-02 application
CN102516423A (en) 2012-06-27 application
JP2008509274A (en) 2008-03-27 application
KR20070051272A (en) 2007-05-17 application
CN1993391A (en) 2007-07-04 application
US8173569B2 (en) 2012-05-08 grant
US9133287B2 (en) 2015-09-15 grant
ES2535821T3 (en) 2015-05-18 grant
EP1778746A1 (en) 2007-05-02 application
US20080076951A1 (en) 2008-03-27 application
EP1778744B1 (en) 2015-03-25 grant
WO2006023057A1 (en) 2006-03-02 application
RU2007108542A (en) 2008-09-20 application
CN101001890A (en) 2007-07-18 application
RU2377256C2 (en) 2009-12-27 grant
CA2574364C (en) 2012-11-27 grant
JP5363728B2 (en) 2013-12-11 grant

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