WO1999054339A1 - Metallocenes comprenant des substituants fluores - Google Patents

Metallocenes comprenant des substituants fluores Download PDF

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Publication number
WO1999054339A1
WO1999054339A1 PCT/EP1999/002561 EP9902561W WO9954339A1 WO 1999054339 A1 WO1999054339 A1 WO 1999054339A1 EP 9902561 W EP9902561 W EP 9902561W WO 9954339 A1 WO9954339 A1 WO 9954339A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyclopentadienyl
different
same
trifluoroethyl
dichloride
Prior art date
Application number
PCT/EP1999/002561
Other languages
German (de)
English (en)
Inventor
Cornelia Fritze
Gerhard Erker
Johannes Ruwwe
Original Assignee
Targor Gmbh
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
Priority claimed from DE1998117728 external-priority patent/DE19817728A1/de
Priority claimed from DE1998117727 external-priority patent/DE19817727A1/de
Application filed by Targor Gmbh filed Critical Targor Gmbh
Priority to JP2000544677A priority Critical patent/JP2002512251A/ja
Priority to EP99920683A priority patent/EP1073665A1/fr
Publication of WO1999054339A1 publication Critical patent/WO1999054339A1/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

  • the present invention relates to metallocenes with fluorine-containing substituents and a process for their preparation and their use.
  • Perfluorinated ligands play an important role in the stabilization of electron-deficient metal centers.
  • the stabilization of cationic metallocenes in Ziegler-Natta polymerization is carried out by perfluorinated tetraphenylborates (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41, 1220).
  • the present invention relates to metallocenes with fluorine-containing substituents and a process for their preparation and their use.
  • the compound according to the invention is an organometallic compound of the formula 0)
  • M ⁇ is a metal from group 3, 4, 5 or 6 of the periodic table of the elements and also lanthanides or actinides,
  • R1 are the same or different and represent a hydrogen atom, a C1-C30 - carbon-containing group such as C-
  • Cyclohexyl or octyl C2-C25-alkenyl, C3-C ⁇
  • C3o-alkylaryl C-
  • R 2 are the same or different and are fluorine-containing C-
  • L are the same or different and represent a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms, e.g. B. C- ⁇ -C20-alkyl, C2-C20-alkenyl, C ⁇ -C2rj-alkoxy, Cß-C ⁇ aryloxy or
  • Z examples are groups M 2 R 4 R5, where M 2 is carbon, silicon, germanium or tin and R 4 and R 5 are identical or different and are C1-C20- 4
  • Hydrocarbon group such as C ⁇
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9) C (CH 3 ) 2, C (CH 3 ) 2 ,
  • Z can also form a mono- or polycyclic ring system with one or more R1 and / or R 2 radicals.
  • Chiral bridged metallocenes of the formula I are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted so that they represent an indenyl ring.
  • the indenyl ring is preferably substituted, in particular in the 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2,4,5,6-position, with C1-C20 carbon-containing Groups such as C 1 -C 8 -alkyl or C 6 -C 20 aryl, where two or more substituents of the indenyl ring can together form a ring system.
  • M ⁇ a metal of group 4 of the periodic table of the elements such as Ti, Zr, or Hf, R1 are the same or different and a hydrogen atom is a C1-C30 - carbon-containing group such as -C-C25-alkyl, in particular methyl, ethyl, tert-butyl, Cyclohexyl or octyl, C2-C25-alkenyl, C3-Ci5-alkylalkenyl, CQ-C24-aryl, C5-C24-heteroaryl such as pyridyl, furyl or quinolyl, C7-C30-
  • R 1 radicals can be linked to one another such that the R 1 radicals and the 5 they connecting atoms of the cyclopentadienyl ring form a C4-C24 ring system, which in turn can be substituted
  • R 2 are the same or different and a fluorine-containing C -C25-alkyl fluorine-containing C-
  • organometallic compound according to the invention examples but not limiting examples are:
  • Dimethylsiiandiyl ( ⁇ 5-3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5-cyclopentadienyl) titanium dichloride
  • Dimethylsilandiyl ( ⁇ 5 -3- (1 ⁇ , 1 ⁇ , 2 ⁇ , 2 ⁇ -perfluorooctyl) cyclopentadienyl ) ( ⁇ 5-cyclopentadienyI) titanium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ⁇ , 2 ⁇ , 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5-3-butylcyclopentadienyl) titanium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ⁇ , 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5-3-butyl-cyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyl ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -3-methyl-cyclopentadienyl) titanium dichloride
  • 2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ⁇ , 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5-3-methyl-cyclopentadienyl) titanium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (2 ' , 2', 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -3-methylcyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ' H, 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5-cyclopentadienyl) zirconium dichloride
  • 1,2-ethanediyl ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5-cyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ⁇ , 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5 -cyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (2 ' , 2', 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5-3-methyl-cyclopentadienyl) titanium dichloride
  • 1,2-ethanediyl ( ⁇ 5 - 3- (2 ' , 2', 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -3-butylcyclopentadienyl) hafnium dichloride
  • Dimethylsilanediylbis ( ⁇ 5 -3- (1 ⁇ , 1 ' H, 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) - titanium dichloride
  • Dimethylsilanediylbis ( ⁇ 5 -3- (1 ⁇ , 1 ⁇ , 2 ' H, 2 ' H-perfluorooctyl ) cyclopentadienyl) zirconium dichloride
  • Dimethylsilanediylbis ( ⁇ 5-3- (1 ⁇ , 1 ' H, 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) - hafnium dichloride ( ⁇ 5 -2 ' , 2 ' , 2 ' , -trifluorethyl) cyclopentadienyl) ( ⁇ 5-butylcyclopentadienyl) titanium dichloride
  • the dimethyl compounds are also important.
  • the compound of the formula (I) according to the invention is prepared by reacting a substituted cyclopentadienide (II), which is obtained from the reaction of metallocene with a fluorine- and iodine-containing alkyl, with metal compound (III) and is to be illustrated by way of example by the reaction scheme below . 13
  • M 1 , R 1 , R 2 , L, Z, m, n, q, r, s, t, v and x have the same meaning as given in formula (I) above, y is the same 1 or 2 and M is a metal, nickel is particularly preferred.
  • the base is a strong base such as butyllithium or potassium hydride.
  • the reaction takes place at temperatures from -50 ° C to + 150 ° C, preferably at 0 ° C to 100 ° C in organic solvents such as toluene, benzene, methylene chloride, carbon tetrachloride, tetrahydrofuran, diethyl ether and gasoline.
  • the implementation takes from 1 min to 20 days.
  • the compound of formula (I) according to the invention can be isolated or used directly for further reactions.
  • the compound of the formula (!) According to the invention can also be prepared in a one-pot reaction without isolation of intermediate and final stages.
  • transition metal compounds according to the invention are highly active 14 catalyst components for the polymerization of olefins to polyolefins (G.
  • olefins examples include 1-olefins such as ethene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1, 3-butadiene, 1, 4 - Hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene and cyclic otefins such as norbornene, tetracyclododecene or methyl norbomene.
  • mixtures of the above olefins can also be copolymerized.
  • the polymerization is carried out at a temperature of -60 ° C to 300 ° C, preferably 50
  • the pressure is 0.5 bar to 2000 bar, preferably 5 bar to 64 bar.
  • the polymerization can be carried out continuously or batchwise, in one or more stages, in a solvent mixture.
  • suitable solvent mixtures include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, cycloalkanes such as cyclopentane and cyclohexane, and aromatics such as benzene, toluene.
  • alkanes such as pentane, isopentane, hexane, heptane, octane and nonane
  • cycloalkanes such as cyclopentane and cyclohexane
  • aromatics such as benzene, toluene.
  • Cycloalkanes such as perfluoro (methylcyclohexane). That is very particularly preferred 15
  • the mixing ratio is 1: 1 to 100: 1, particularly preferably 1: 1 to 10: 1, particularly preferably 1: 1.
  • an aluminum alkyl for example trimethyl aluminum, triethyl aluminum or
  • Triisobutyl aluminum advantageous. This cleaning can take place both in the polymerization system itself, or the olefin is brought into contact with the Al compound before the addition into the polymerization system and then separated again.
  • hydrogen is added as a molecular weight regulator and / or to increase the activity.
  • another alkylaluminium compound such as trimethylaluminum, triethylaluminium, triisobutylaluminum, trioctylaluminum or isoprenylaluminum, can be used to render the polymerization system inert (for example to separate the catalyst from the olefin in the reactor) are given. This is in a concentration of 100 to 0.01 mmol AI per kg
  • Triisobutyl aluminum and triethyl aluminum are preferably used in a concentration of 10 to 01 mmol Al per kg reactor content.
  • the present invention also relates to a process for the preparation of polyolefins by polymerizing one or more olefins in the presence of at least one metallocene of the formula (I)
  • the polymers produced with the catalyst system according to the invention have a uniform grain morphology and have no fine grain fractions. No deposits or caking occur during the polymerization with the catalyst system according to the invention.
  • the polymers produced by the process according to the invention are particularly suitable for producing tear-resistant, hard and rigid moldings such as fibers, filaments, injection molded parts, foils, plates or large hollow bodies such as pipes.
  • the compounds were characterized by ⁇ H-HMR, 19F-NMR, DSC analysis.
  • a solution of 0.98 g of 1 ' H, 1 ' H, 2 ' H, 2 ' H-perfluorooctylcyclopentadiene from Example 5 in 60 ml of tetrahydrofuran is mixed with 1.49 ml of 1.65M butyllithium solution at -78 ° C and cooled with a Suspension of 0.426 g of zirconium tetrachloride-THF adduct in 40 ml of tetrahydrofuran.
  • the mixture is allowed to warm to room temperature and the solvent is removed in vacuo.
  • the product is extracted using
  • Pentamethylcyclopentadienylzirconium trichloride in 30 ml of tetrahydrofuran was prepared by Pentamethylcyclopentadienylzirconium trichloride in 30 ml of tetrahydrofuran.
  • the mixture is allowed to warm to room temperature and the solvent is removed in vacuo.
  • the product is isolated by extraction with methylene chloride and pentane.
  • Product is isolated by extraction with pentane.

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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 métallocènes comprenant des substituants fluorés, leur utilisation dans la polymérisation d'oléfines et un procédé de production de polyoléfines à l'aide desdits métallocènes.
PCT/EP1999/002561 1998-04-21 1999-04-16 Metallocenes comprenant des substituants fluores WO1999054339A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2000544677A JP2002512251A (ja) 1998-04-21 1999-04-16 フッ素含有置換基を含むメタロセン
EP99920683A EP1073665A1 (fr) 1998-04-21 1999-04-16 Metallocenes comprenant des substituants fluores

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE1998117728 DE19817728A1 (de) 1998-04-21 1998-04-21 Metallocene mit fluorhaltigen Substituenten
DE19817728.3 1998-04-21
DE19817727.5 1998-04-21
DE1998117727 DE19817727A1 (de) 1998-04-21 1998-04-21 Verwendung von Metallocenen mit fluorhaltigen Substituenten

Publications (1)

Publication Number Publication Date
WO1999054339A1 true WO1999054339A1 (fr) 1999-10-28

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EP (1) EP1073665A1 (fr)
JP (1) JP2002512251A (fr)
WO (1) WO1999054339A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2434959T3 (es) 2007-11-19 2013-12-18 Mitsui Chemicals, Inc. Catalizador de la polimerización de olefinas con metaloceno en puentes y polímero de etileno obtenido usando el catalizador
JP5405806B2 (ja) * 2007-11-19 2014-02-05 三井化学株式会社 オレフィン重合用触媒およびそれを用いたエチレン系重合体の製造方法
JP2009197226A (ja) * 2008-01-25 2009-09-03 Mitsui Chemicals Inc エチレン共重合体、該エチレン共重合体を含む熱可塑性樹脂組成物およびこれらから得られる成形体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JANY, G. ET AL.: "para-Fluoro benzyl substituted bis(indenyl) metallocenes as catalyst precursors in ethene polymerization", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 553, 25 February 1998 (1998-02-25), pages 173 - 178, XP004119631 *

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JP2002512251A (ja) 2002-04-23
EP1073665A1 (fr) 2001-02-07

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