WO1999045014A1 - Composes metallocenes avec ligand bis(2,5-disubstitue-3-phenylcyclopentadienyle) et son procede de production - Google Patents

Composes metallocenes avec ligand bis(2,5-disubstitue-3-phenylcyclopentadienyle) et son procede de production Download PDF

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Publication number
WO1999045014A1
WO1999045014A1 PCT/JP1999/001016 JP9901016W WO9945014A1 WO 1999045014 A1 WO1999045014 A1 WO 1999045014A1 JP 9901016 W JP9901016 W JP 9901016W WO 9945014 A1 WO9945014 A1 WO 9945014A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
group
zirconium dichloride
bis
butyl
Prior art date
Application number
PCT/JP1999/001016
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English (en)
Japanese (ja)
Inventor
Seiki Mitani
Akiko Kageyama
Masato Nakano
Jun Saito
Hiroshi Yamazaki
Original Assignee
Chisso Corporation
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
Application filed by Chisso Corporation filed Critical Chisso Corporation
Priority to AU27453/99A priority Critical patent/AU2745399A/en
Priority to DE19983021T priority patent/DE19983021T1/de
Publication of WO1999045014A1 publication Critical patent/WO1999045014A1/fr

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Classifications

    • 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

Definitions

  • Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl, (2,5-dimethylphenyl) methyl, (2,6-dimethylphenyl) methyl, (2,3,4-trimethylphenyl) methyl, (2,3,5-trimethylphenyl) methyl, (2,3 , 6-trimethylphenyl) methyl, (ethylphenyl) methyl, (propylphenyl) methyl, (butylphenyl) methyl, naphthylmethyl, and anthrylmethyl, and halogenated aralkyl groups in which these groups are further substituted with halogen atoms. Is also included.
  • substituted silyl groups include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-i-propylsilyl, tri-n-butylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl, triflunil. And silyl.
  • R 1 is n-propyl
  • R 6 is fluorine
  • R 4 , RR 7 and R 8 are hydrogen, di (n-propyl) silylenebis [2,5-dimethyl-3- ( P-fluorophenyl) cyclopentene zirconium dichloride, Di (n-propyl) silylenebis [2,5-diethyl-3- (P-fluorophenyl) -cyclopentagenenyl] zirconium dichloride, di (n-propyl) silylenebis [2,5-di ( n-propyl) 1-3- (p-fluorophenyl) 1-cycle pentagenenyl] zirconium dichloride, di (n-propyl) silylene bis
  • Y is germanium
  • R 1 is ethyl
  • R 6 is methoxy
  • R 4 , R 5 , R 7 and R 8 are hydrogen
  • Examples where Y is germanium, R 1 is phenyl, R 6 is i-propyl, and R 4 , R 5 , R 7 and R 8 are hydrogen are diphenylgermylene bis [2,5-dimethyl-3 — (P— ( i-Propyl) phenyl) -cyclopentagenenyl] zirconiumdi Chloride, diphenylgermylene bis [2,5-getyl-13- (p- (i-propyl) phenyl) -cyclopentagenenyl] zirconium dichloride, diphenylgermylene bis [2,5-di (n-propyl) 1) 3- (p- (i-propyl) phenyl) 1-cyclopentagenenyl] zirconium dichloride, diphenylgermylene bis [2,5-di (i-propyl) 13- (p- (i-propyl) Phenyl) -cyclopentagenenyl] zirconium dichloride
  • cross-linking agent represented by the above general formula (4) examples include dichlorodimethylsilane, dichloromethylethylsilane, dichlorodi- ⁇ -propylsilane, dichlorodi- ⁇ -butylsilane, dichlorodiphenylsilane, and dibumodimethyl.
  • the metal halide used for ring closure of bis (2,5-disubstituted 1-3-phenyl-cyclopentagenenyl) compounds is represented by the general formula (6)
  • X 1 and X 2 may be the same or different, each represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom).
  • the metal halide represented by the general formula (6) include titanium tetrachloride, titanium tetrabromide, titanium tetrodizide, titanium tetrafluoride, methyl titanium trichloride, methyl titanium tribromide, methyl Rutitanium trifluoride, methyl titanium trifluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetriodizide, zirconium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetrachloride And zid and hafnium tetrafluoride.
  • the reaction of a dianionated bis (2,5-disubstituted 1-3-phenyl-1-cyclopentene genyl) compound with the corresponding metal halide is accomplished by dissolving or suspending the metal halide in a solvent and forming the dianionate in it.
  • the reaction is carried out by mixing the prepared bis (2,5-disubstituted 1-3-phenyl-cyclopentagenenyl) compound.
  • meta-mouth compound may be used alone or together with other compounds in a particulate carrier.
  • a granular or spherical inorganic or organic fine particle solid having a particle diameter of 5 to 300, preferably 10 to 200 m is used as such a fine particle carrier. Is done.
  • the olefin which can be polymerized by using the catalyst containing the metallocene compound ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-1hexene, 11-pentene, 1-decene, 1- Linear ⁇ -olefins such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1butene, 4-methyl-1-pentene, 2-methyl-1-pentene And the like, and mixtures of two or more thereof.
  • any of a batch system, a semi-continuous system, and a continuous system may be employed. Further, the polymerization may be performed in two or more stages by changing the reaction conditions.
  • the pressure of the polymerization reaction system is not particularly limited, but is preferably in the range of normal pressure to 5 O kgZcm 2 .
  • the polymerization temperature is not particularly limited, but is usually in the range of 150 to 250 ° C, preferably in the range of 130 to 100 ° C.
  • the molecular weight at the time of polymerization can be adjusted by known means, for example, selection of temperature or introduction of hydrogen. The following examples further illustrate the invention.
  • the obtained crystals were recrystallized from a mixed solution of toluene and hexane to obtain 2.3 g of dimethylrylenebis (2,5-dimethyl-3- (p-tolyl) -cyclopentagenenyl) zirconium dichloride.
  • the 1 H-NMR spectrum data of the obtained crystals showed that the ratio of the racemic nomeso was a mixture of 96-4.
  • propylene was introduced at a pressure of 0.3 MPa, and polymerization was performed for 1 hour. After polymerization, the polypropylene was filtered, and the catalyst component was decomposed with 2 liters of hydrochloric methanol. This was filtered, washed and dried in that order to obtain 68 g of polypropylene.

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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 des composés métallocènes racémiques représentés par la formule générale (1), et des composés mésométallocènes représentés par la formule générale (2). Dans ces formules, M représente titane, zirconium ou hafnium; Y représente carbone, silicium, germanium, ou étain; X1 et X2 représentent chacun halogéno ou un groupe hydrocarboné; R2 et R3 représentent chacun halogéno, alkyle, aralkyle, aryle, silyle à substitution hydrocarbure, alkoxy, aralkyloxy, ou aryloxy; et R?1, R4, R5, R6, R7 et R8¿ représentent chacun hydrogène, halogéno, alkyle, aralkyle, aryle, silyle à substitution hydrocarbure, alkoxy, aralkyloxy, ou aryloxy.
PCT/JP1999/001016 1998-03-05 1999-03-03 Composes metallocenes avec ligand bis(2,5-disubstitue-3-phenylcyclopentadienyle) et son procede de production WO1999045014A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU27453/99A AU2745399A (en) 1998-03-05 1999-03-03 Metallocene compounds having bis(2,5-disubstituted-3-phenylcyclopentadienyl) ligand and process for producing the same
DE19983021T DE19983021T1 (de) 1998-03-05 1999-03-03 Metallocenverbindungen mit Bis(2,5-disubstituiertem-3-Phenyl-cyclopentadienyl)-Ligand und Verfahren zur Herstellung derselben

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/53340 1998-03-05
JP5334098 1998-03-05

Publications (1)

Publication Number Publication Date
WO1999045014A1 true WO1999045014A1 (fr) 1999-09-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/001016 WO1999045014A1 (fr) 1998-03-05 1999-03-03 Composes metallocenes avec ligand bis(2,5-disubstitue-3-phenylcyclopentadienyle) et son procede de production

Country Status (3)

Country Link
AU (1) AU2745399A (fr)
DE (1) DE19983021T1 (fr)
WO (1) WO1999045014A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010055935A1 (fr) * 2008-11-11 2010-05-20 Sumitomo Chemical Company, Limited Copolymère éthylène-α-oléfine et objet moulé à base de ce polymère
JP2010138385A (ja) * 2008-11-11 2010-06-24 Sumitomo Chemical Co Ltd エチレン−α−オレフィン共重合体及び成形体
WO2012117823A1 (fr) 2011-03-02 2012-09-07 株式会社Adeka Procédé de fabrication d'un film stratifié et composition de résine pour le revêtement d'éléments
WO2013140905A1 (fr) 2012-03-23 2013-09-26 株式会社Adeka Procédé de fabrication d'une composition de résine oléfinique pour des matières pour appareils électriques et des matières d'intérieur d'automobile
WO2015060257A1 (fr) 2013-10-21 2015-04-30 株式会社Adeka Procédé de production d'un polymère stabilisé
EP3042990A1 (fr) 2010-11-16 2016-07-13 Adeka Corporation Procédé de stabilisation à long terme d'un polymère, procédé de fabrication d'un tissu non tissé et procédé de production d'une composition élastomère

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04211694A (ja) * 1990-02-26 1992-08-03 Basf Ag Ｃ２−ｃ１０アルケン−１重合体用の可溶性触媒組成物
WO1997003081A1 (fr) * 1995-07-11 1997-01-30 Basf Aktiengesellschaft Procede de transformation de la meso-forme achirale ou d'un racemate d'un complexe ansa-metallocene ou de ses melanges en un de ses enantiomeres
WO1997003080A1 (fr) * 1995-07-11 1997-01-30 Basf Aktiengesellschaft Procede de transformation de la meso-forme achirale d'un complexe ansa-metallocene en la forme racemique chirale

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04211694A (ja) * 1990-02-26 1992-08-03 Basf Ag Ｃ２−ｃ１０アルケン−１重合体用の可溶性触媒組成物
WO1997003081A1 (fr) * 1995-07-11 1997-01-30 Basf Aktiengesellschaft Procede de transformation de la meso-forme achirale ou d'un racemate d'un complexe ansa-metallocene ou de ses melanges en un de ses enantiomeres
WO1997003080A1 (fr) * 1995-07-11 1997-01-30 Basf Aktiengesellschaft Procede de transformation de la meso-forme achirale d'un complexe ansa-metallocene en la forme racemique chirale

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010055935A1 (fr) * 2008-11-11 2010-05-20 Sumitomo Chemical Company, Limited Copolymère éthylène-α-oléfine et objet moulé à base de ce polymère
JP2010138385A (ja) * 2008-11-11 2010-06-24 Sumitomo Chemical Co Ltd エチレン−α−オレフィン共重合体及び成形体
US8436101B2 (en) 2008-11-11 2013-05-07 Sumitomo Chemical Company, Limited Ethylene-α-olefin copolymer and molded object thereof
EP3042990A1 (fr) 2010-11-16 2016-07-13 Adeka Corporation Procédé de stabilisation à long terme d'un polymère, procédé de fabrication d'un tissu non tissé et procédé de production d'une composition élastomère
WO2012117823A1 (fr) 2011-03-02 2012-09-07 株式会社Adeka Procédé de fabrication d'un film stratifié et composition de résine pour le revêtement d'éléments
EP2966095A1 (fr) 2011-03-02 2016-01-13 Adeka Corporation Procédé de production d'une composition de résine pour revêtement d'éléments
WO2013140905A1 (fr) 2012-03-23 2013-09-26 株式会社Adeka Procédé de fabrication d'une composition de résine oléfinique pour des matières pour appareils électriques et des matières d'intérieur d'automobile
WO2015060257A1 (fr) 2013-10-21 2015-04-30 株式会社Adeka Procédé de production d'un polymère stabilisé

Also Published As

Publication number Publication date
DE19983021T1 (de) 2001-02-15
AU2745399A (en) 1999-09-20

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