WO2004067586A2 - Systemes catalytiques a metaux de transition melanges pour la polymerisation de monomeres polymerisables - Google Patents

Systemes catalytiques a metaux de transition melanges pour la polymerisation de monomeres polymerisables Download PDF

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Publication number
WO2004067586A2
WO2004067586A2 PCT/EP2003/013774 EP0313774W WO2004067586A2 WO 2004067586 A2 WO2004067586 A2 WO 2004067586A2 EP 0313774 W EP0313774 W EP 0313774W WO 2004067586 A2 WO2004067586 A2 WO 2004067586A2
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WO
WIPO (PCT)
Prior art keywords
group
bis
formula
ethyl
sime2
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.)
Ceased
Application number
PCT/EP2003/013774
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English (en)
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WO2004067586A3 (fr
Inventor
Ludovic Pronko
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.)
Safetec GmbH
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Safetec GmbH
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Publication date
Application filed by Safetec GmbH filed Critical Safetec GmbH
Priority to AU2003296617A priority Critical patent/AU2003296617A1/en
Publication of WO2004067586A2 publication Critical patent/WO2004067586A2/fr
Publication of WO2004067586A3 publication Critical patent/WO2004067586A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not

Definitions

  • EP-A-0 250 999 relates to the preparation of branched linear polyethylene by oligomerisation of ethylene using a nickel containing catalyst and polymerisation of the obtained oligomers in the presence of ethylene by means of a chromium based catalyst.
  • the process requires the use of two individual catalyst components.
  • WO 97/48735 discloses a mixed catalyst systems comprising a late transition metal catalyst system and a catalyst system selected from a late transition metal catalyst system, metallocene catalyst system and conventional Ziegler-Natta catalyst system.
  • the subject-matter of the present invention is a metallocene compound of the general formula (I): L 1 n YZ M ! X p (I) wherein
  • X and D being a monovalent ligand, are each independently selected from a hydrogen atom, a halogen atom, aR 27 group, OR 27 , OSO 2 CF 3 , OCOR 27 , SR 27 , NR 2 27 or PR 2 27 group, wherein the substituents R 27 are defined as R 1 ; is 1, 2 or 3.
  • Y is equal to Z, both being a group selected of formula (Ila), (Lib),
  • R 29 to R 34 are each independently selected from hydrogen and an aliphatic and aromatic hydrocarbon group, optionally containing a heteroatom selected from the group 13-16 of the
  • Y is selected from a group of formula (Ila), (lib), (Ilia) and (Illb) and Z is an unsubstituted or substituted cyclopentadienyl group containing 1-4 hydrocarbyl groups, such as methyl, ethyl, isopropyl, tert-butyl, such as tetramethyl cyclopentadien, optionally substituted by a heteroatom such as silicon (trimethylsilyl) and/or nitrogen.
  • the cyclopentadienyl group can be mono, di, tri and tetr alkylated.
  • SiMe2 ⁇ 6-[2,7-bis(l-(2-ter-butylphenylimino)ethyl)pyrido[d]cyclopentadienyl iron pi]C12]- l-(indenyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis(l-(2,6-diethylphenyhmino)ethyl>pyrido[d]cyclopentadienyl iron pi]C12]- l-(2-methyl-4-na ⁇ htyl-indenyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis(l-(2,6-diter-butylphenyHmino)ethyl)pyrido[d]cyclopentadienyl iron pi]C12]-l-(3-methyl-indenyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis( l-(2,6-diisopropylphenylimino)ethyl)pyrido[d]cyclopentadienyl iron pi]Cl2]-l-(3-trimethylsilyl-indenyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis( 1 -(2,6-diisopropylphenylimino)ethyl)pyrido[d]cyclopentadienyl iron pi]C12]-l-(2,4-dimethyl-indenyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis(l-(2,6-(-liisopropylphenylimino)ethyl)pyrido[d]cyclopentadienyl iron pi]C12]-l-(£luorenyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis(l-(2,6-diethylphenylimino)ethyl)pyrido[d]cyclopentadienyl iron pi]Cl2]- l-(cyclopentadienyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis(l-(2,6-diisopropylphenylimino)ethyl>pyrido[d]cyclopentadienyl iron pi]C12]-l-(cyclopentadienyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis(l-(2-isopropylphenylimino)ethyl)pyrido[d]cyclopentadienyl iron pi]C12]-l-(3-nbutyl-cyclopentadienyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis( l-(2,6-dimethylphenyHmino)ethyl)pyrido[d]cyclopentadienyl iron pI]C12] 1 -(3-nbutyl-cyclopentadienyl) ⁇ ZrC12;
  • SiMe2 ⁇ 6-[2,7-bis ⁇ l-(2,6-diethylphenylimino)ethyl>pyrido[d]cyclopentadienyl iron pi]C12]- l-(tetramethyl-cyclopentadienyl) ⁇ ZrC12;
  • SiMe 2 ⁇ [2,6-bis(l-(2,6-diter-butylphenylimino)ethyl)4-pyridinyl iron pi]C12](5- cyclopentadienyl)methan ⁇ ⁇ cyclopentadienyl ⁇ ZrC12;
  • SiMe2 ⁇ [2,6-bis(l-(2,6-di-i-propylphenyHmino)ethyl)4-pyridinyl iron pi]C12](5- cyclopentadienyl)methan ⁇ ⁇ cyclopentadienyl ⁇ ZrC12; SiMe2 ⁇ l,l-[2,6-bis(l-(2,6-diter-butylphenyhmino)ethyl>4-pyridinyl iron pi]C12](5- cyclopentadienyl)ethan ⁇ ⁇ cyclopentadienyl ⁇ ZrC12;
  • SiPhMe, CPh 2 , or CPhMe, PH 2 , PMe 2 , NH, NR, group, or the metallocene compounds are unbridged.
  • n-butyl radical attached to the cyclopentadienyl moiety is substituted by a tert- butyl radical or trimethylsilyl.
  • Another subject-matter of the present invention is a metallocene compound of the general formula (T):
  • R 15 to R 17 , L 3 and n have the same meaning as described above and Y ⁇ is selected from a group of (Illb)
  • Non-limiting examples of the metallocene of formula (T) are the corresponding compounds of formula (I) as examplified above with the exception that the compounds do not contain the late transition metals M 2 and M 3 .
  • a further subject-matter of the present application is the provision of a process for the
  • the oHgomerisation is carried out in a temperature range of -10 to 300° C, preferably between 10 and 200°C and most preferably between 60 and 150 ° C.
  • the polymerisation is carried out at a pressure of at least 1 bar, preferably between 5 and 1500 bar, most preferably between
  • the catalyst components of the present invention are also useful for the copolymerisation of ethylene or alpha-olefins with polar monomers such as (meth)acrylate.
  • the process of the present invention is also useful for the preparation of blends containing polypropylene and LDPE.
  • the process of the present invention is also useful for the preparation of blends containing polypropylene and partially crosslinked polybutadiene, polymethacrylates and also acrylate grafted polypropylene.
  • the compositions obtained thereof are excellent in mouldabiHty.
  • the films obtained thereof have high transparancy and high mechanical strenght.
  • a further subject-matter of the present invention is a polymer composition obtainable by a process according to the present invention.
  • blends can contain additionally to the above elastomers LDPE, LLDPE and HDPE.
  • the polymerisation is carried out in gas phase- or slurry polymerisation when reactor blends containing branched and linear polyethylene is desired.
  • reactionand the reaction conditions are similar to that described in WO 93/08199.

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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)

Abstract

L'invention concerne un constituant catalytique servant à préparer des polyoléfines et comprenant un métallocène de formule générale L1nYZM1XP (I) dans laquelle les symboles ont la signification définie dans la description. L'invention concerne également des catalyseurs contenant ce constituant catalytique, un procédé pour préparer ce métallocène et un procédé pour produire des polyoléfines en présence de ce catalyseur.
PCT/EP2003/013774 2002-12-09 2003-12-05 Systemes catalytiques a metaux de transition melanges pour la polymerisation de monomeres polymerisables Ceased WO2004067586A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003296617A AU2003296617A1 (en) 2002-12-09 2003-12-05 Mixed bimetallic olefin polymerisation catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MT181702 2002-12-09
MTPAT-1817 2002-12-09

Publications (2)

Publication Number Publication Date
WO2004067586A2 true WO2004067586A2 (fr) 2004-08-12
WO2004067586A3 WO2004067586A3 (fr) 2004-12-29

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PCT/EP2003/013774 Ceased WO2004067586A2 (fr) 2002-12-09 2003-12-05 Systemes catalytiques a metaux de transition melanges pour la polymerisation de monomeres polymerisables

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AU (1) AU2003296617A1 (fr)
WO (1) WO2004067586A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008077530A3 (fr) * 2006-12-22 2008-09-04 Basell Polyolefine Gmbh Composition de polyéthylène multimodale, catalyseur mixte et procédé de préparation de la composition
US8309780B2 (en) 2007-12-21 2012-11-13 Exxonmobil Research And Engineering Company Process for making olefin oligomers and alkyl benzenes in the presence of mixed metal oxide catalysts

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1160384C (zh) * 2001-12-10 2004-08-04 中国科学院长春应用化学研究所 高分子化双活性中心烯烃聚合催化剂的制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CHEMABS [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 10 December 2001 (2001-12-10), JIN, GUOXIN ET AL: "Preparation of polymeric catalyst with double active sites for olefin polymerization" XP002277484 retrieved from STN Database accession no. 2003:600096 & CN 1 352 204 A (CHANGCHUN RESEARCH INSTITUTE OF APPLIED CHEMISTRY, THE CHINESE ACADEMY) 5 June 2002 (2002-06-05) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008077530A3 (fr) * 2006-12-22 2008-09-04 Basell Polyolefine Gmbh Composition de polyéthylène multimodale, catalyseur mixte et procédé de préparation de la composition
US8722833B2 (en) 2006-12-22 2014-05-13 Basell Polyolefine Gmbh Multimodal polyethylene composition, mixed catalyst and process for preparing the composition
US8309780B2 (en) 2007-12-21 2012-11-13 Exxonmobil Research And Engineering Company Process for making olefin oligomers and alkyl benzenes in the presence of mixed metal oxide catalysts

Also Published As

Publication number Publication date
AU2003296617A1 (en) 2004-08-23
AU2003296617A8 (en) 2004-08-23
WO2004067586A3 (fr) 2004-12-29

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