CA2371835A1 - Stereorigid, bridged metallocene catalysts for polyolefin production - Google Patents

Stereorigid, bridged metallocene catalysts for polyolefin production Download PDF

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Publication number
CA2371835A1
CA2371835A1 CA002371835A CA2371835A CA2371835A1 CA 2371835 A1 CA2371835 A1 CA 2371835A1 CA 002371835 A CA002371835 A CA 002371835A CA 2371835 A CA2371835 A CA 2371835A CA 2371835 A1 CA2371835 A1 CA 2371835A1
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use according
polyolefin
substituent
hydrogen
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CA002371835A
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CA2371835C (en
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Abbas Razavi
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TotalEnergies One Tech Belgium SA
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    • 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
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/15—Isotactic
    • 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
    • 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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

Use of a metallocene catalyst component for the preparation of a polyolefin which comprises an isotactic or polyolefin syndiotactic/isotactic block polyolefin having a monomer length of up to C10, which component has the general formula:
R"C p R1R2R3)(C p'R1'R2')MQZ wherein Cp is a cyclopentadienyl ring substituted with at least one substituent; C p' is a substituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; R1 is optionally a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group IVA, and each R$ is the same of different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R1' and R2' are each independently substituent groups on the fluorenyl ring, one of which is a group of the formula AR'''3, in which A is chosen from Group IVA, and each R''' is independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms and the other is hydrogen or a second group of the formula AR'''3; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having I to 20 carbon atoms or is a halogen.

Claims (31)

  1. Claim 1.
    Use of a metallocene catalyst component for the prepation of a polyolefin which comprises an isotactic polyolefin or syndiotactic/sotactic block polyolefin having a monomer length of up to C10, which component has the general formula:
    R"(C p R1R2R3)(C p R1R2)MQ2 Wherein C p is a cyclopentadienyl ring substituted with at feast one substituent; C p' is a substituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; R1 is hydrogen or a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR"3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is hydrogen or a substituent on the cyclopentadienly ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is hydrogen or a substituent on the cyclopentadienly ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group NA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, with the proviso that at least one of R1, R2 or R3 is not hydrogen; R1' and R2' are each independently substituent groups on the fluorenyl ring, one of which is a group of the formula AR'''3, in which A is chosen from Group IVA, and each R''' is independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms and the other is hydrogen or a second group of the formula AR'''3; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.
  2. 2. Use according to claim 1, wherein R1' and R2' are at positions 3 and 6 on the fluorenyl ring.
  3. 3. ose according to claim 1 or claim 2, wherein A is carbon or silicon.
  4. 4. Use according to claim 3, wherein AR'''3 is hydrocarbyl having from 1 to 24 carbon atoms.
  5. 5. Use according to claim Q, wherein: AR''' 3 is C (CH3)3.
  6. 6. Use according to claim 2, wherein AR''' 3 is Si(CH3)3.
  7. 7. Use according to any one of the preceding claims, wherein R1' and R2' are the same.
  8. 8. Use according to any one of the preceding claims, wherein R" is alkylidene having 1 to 20 carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphine or amine.
  9. 9. Use according to claim 8, wherein R" is isopropylidene, dimethylsilanediyl or diphenylmethylidene.
  10. 10. Use according to any one of the preceding claims, wherein M is zirconium or titanium.
  11. 11. Use according to any one of the preceding claims, wherein Q is halogen.
  12. 12. Use according to any one of the preceding claims, wherein R1 is C(CH3)3, C(CH3)2Ph, CPh3 or Si(CH3)3.
  13. 13. Use according to claim 12, wherein R1 is C(CH3)3.
  14. 14. Use according to any one of the preceding claims, wherein Y is carbon.
  15. 15. Use according to any one of the preceding claims, wherein 2 is carbon.
  16. 16. Use according to any preceding claim, wherein R2 is CH3.
  17. 17. Use according to any one of the preceding claims, wherein R3 is CH3.
  18. 18. Use according to any one of the preceding claims, wherein the metallocene catalyst component comprises isopropylidene-3-t-butyl-5-methyl-cyclopentadienyl 3,6 di t-butyl fluorenyl ZrCl2.
  19. 19. Use according to any one of the preceding claims, wherein the metallocene catalyst component comprises (i) a catalyst component according to any one of the preceding claims; and (ii) a regioisomer thereof in which R2 is proximal to the bridge and positioned vicinal to the distal substituent.
  20. 20. Use according to any one of claims 1 to 17, wherein the metallocene catalyst component comprises isopropylidene-(3-t-butyl-5-methyl cyclopentadienyl-3,6 di t-butyl fluorenyl) ZrCl2 and isopropylidene-(3-t-butyl-2-methyl cyclopentadienyl-3,6 di t-butyl fluorenyl) ZrCl2.
  21. 21. Use according to any one of the preceding claims, wherein the catalyst component is part of a catalyst system which further comprises an aluminium- or boron-containing co-catalyst capable of activating the catalyst component.
  22. 22. Use according to claim 17, wherein the catalyst system further comprises an inert support.
  23. 23. Use according to any one of claims 1 to 13, wherein R1 is a substituent on the cyclopentadienyl ring and the polyolefin is a syndiotactic/isotactic block polyolefin.
  24. 24. Use according to any one of claims 1 to 17, wherein R1 and R2 are both substituents on the cyclopentadienyl ring and the polyolefin is an isotactic polyolefin.
  25. 25. Use according to claim 19 or claim 20, wherein the polyolefin comprises an isotactic polyolefin having a multimodal molecular weight distribution.
  26. 26. A process for preparing polyolefins having a monomer length of up to C10, which comprises contacting a catalyst system as defined in claim 21 or claim 22 with at least one olefin in a reaction zone under polymerisation conditions to Corm an isotactic polyolefin or a syndiotactic/isotactic block polyolefin.
  27. 27. A process according to claim 26, wherein the olefin is propylene.
  28. 28. A process according to claim 26, wherein two or more olefins are present in the reaction zone to produce a polyolefin copolymer.
  29. 29. An isotactic polyolefin having a monomer length of up to C10 a,d a pentad distribution comprising at least 87 % mmmm as measured by 13C NMR, wherein the amount of 2-1 and 1-3 monomer insertions in the polyolefin is undetectable and wherein the weight average molecular weight is at least 450.000.
  30. 30. A polyolefin according to claim 29, wherein the pentad distribution comprises at least 95% mmmm as measured by 13C
    nmr.
  31. 31. A polyolefin according to claim 29 or claim 30, which comprises a polypropylene.
CA2371835A 1999-02-19 2000-02-18 Stereorigid, bridged metallocene catalysts for polyolefin production Expired - Fee Related CA2371835C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/EP1999/001094 WO2000049029A1 (en) 1999-02-19 1999-02-19 Polyolefin production
EPPCT/EP99/01094 1999-02-19
PCT/EP2000/001378 WO2000049056A1 (en) 1999-02-19 2000-02-18 Polyolefin production

Publications (2)

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CA2371835A1 true CA2371835A1 (en) 2000-08-24
CA2371835C CA2371835C (en) 2010-07-27

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JP (1) JP4864176B2 (en)
KR (1) KR100663788B1 (en)
CN (1) CN1152056C (en)
AT (1) ATE271071T1 (en)
AU (2) AU3141199A (en)
BR (1) BR0008312B1 (en)
CA (1) CA2371835C (en)
DE (1) DE60012166T2 (en)
ES (1) ES2223460T3 (en)
RU (1) RU2244721C2 (en)
WO (2) WO2000049029A1 (en)

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US6469188B1 (en) 1999-01-20 2002-10-22 California Institute Of Technology Catalyst system for the polymerization of alkenes to polyolefins
JP4554133B2 (en) * 1999-10-08 2010-09-29 三井化学株式会社 Metallocene compound, method for producing metallocene compound, olefin polymerization catalyst, method for producing polyolefin, and polyolefin
DE60020694T2 (en) * 2000-08-07 2006-05-04 Total Petrochemicals Research Feluy, Seneffe polyolefin
US7081493B2 (en) * 2001-03-15 2006-07-25 Mitsui Chemicals, Inc. Automotive part made of polypropylene resin composition
KR101004338B1 (en) 2003-03-28 2010-12-28 미쓰이 가가쿠 가부시키가이샤 Propylene?1?butene copolymer, polypropylene composition, use thereof, and polypropylene composite film
EP1493778A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Polyolefin production
EP1493759A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Polymerisation process
EP1493760A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Styrene copolymerisation process
EP1496070A1 (en) * 2003-07-09 2005-01-12 Total Petrochemicals Research Feluy A polyolefin having internal double bonds and a method for making the same
JP4823910B2 (en) * 2004-08-30 2011-11-24 三井化学株式会社 Propylene polymer production method
WO2006126610A1 (en) * 2005-05-25 2006-11-30 Mitsui Chemicals, Inc. Transition metal compound, olefin polymerization catalyst, and process for producing olefin polymer
EP1734059A1 (en) * 2005-06-13 2006-12-20 Total Petrochemicals Research Feluy Carbon-bridged cyclopentadienyl-fluorenyl ligands
EP1734058A1 (en) * 2005-06-13 2006-12-20 Total Petrochemicals Research Feluy Ethylene and alpha-olefins polymerisation catalyst system based on fluorenyl ligand
US8017705B2 (en) 2006-11-17 2011-09-13 Mitsui Chemicals, Inc. Process for production of syndiotactic propylene polymer
CN101600743B (en) 2007-01-18 2012-08-29 普瑞曼聚合物株式会社 Propylene homopolymer for stress-resistant molded object, composition containing the polymer, and stress-resistant molded object obtained from the same
US8119553B2 (en) * 2007-09-28 2012-02-21 Chevron Phillips Chemical Company Lp Polymerization catalysts for producing polymers with low melt elasticity
CN105330771B (en) * 2014-12-03 2018-12-14 亚培烯科技（杭州）有限公司 A kind of metallocene linear-low density polyethylene catalyst and its preparation method and application
CN115677879A (en) * 2021-07-31 2023-02-03 华为技术有限公司 Catalyst for preparing cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and application of cycloolefin copolymer

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EP0419677B1 (en) * 1989-04-18 1995-12-27 MITSUI TOATSU CHEMICALS, Inc. Syndiotactic polypropylene resin composition
DE69116814T2 (en) * 1990-11-20 1996-09-26 Mitsubishi Chem Corp Functionalized olefin polymers
US5710222A (en) * 1992-06-22 1998-01-20 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
JPH08325327A (en) * 1995-06-02 1996-12-10 Chisso Corp Highly stereoregular polypropylene
EP0780396B1 (en) * 1995-12-18 2002-10-02 Basell Polyolefine GmbH Process for depleting by-products in reaction mixtures
ATE325821T1 (en) * 1996-08-13 2006-06-15 Basell Polyolefine Gmbh SUPPORTED CHEMICAL COMPOUND
EP0881236A1 (en) * 1997-05-26 1998-12-02 Fina Research S.A. Metallocene catalyst component for use in producing isotactic polyolefins

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KR20020002471A (en) 2002-01-09
DE60012166D1 (en) 2004-08-19
AU2806200A (en) 2000-09-04
ES2223460T3 (en) 2005-03-01
CA2371835C (en) 2010-07-27
JP2002510358A (en) 2002-04-02
BR0008312B1 (en) 2011-06-14
KR100663788B1 (en) 2007-01-03
WO2000049056A1 (en) 2000-08-24
AU3141199A (en) 2000-09-04
CN1346373A (en) 2002-04-24
ATE271071T1 (en) 2004-07-15
CN1152056C (en) 2004-06-02
DE60012166T2 (en) 2005-09-08
RU2244721C2 (en) 2005-01-20
JP4864176B2 (en) 2012-02-01
BR0008312A (en) 2002-01-22
WO2000049029A1 (en) 2000-08-24

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