DE19817726A1 - Catalyst system for production of polypropylene - Google Patents

Abstract

A catalyst system for the polymerization of propylene contains special metallocene(s) with fluorinated substituents, together with cocatalyst(s) and optional support(s) is new. A catalyst system contains: (a) cocatalyst(s); (b) organometallic compound(s) of formula (I); and optionally (c) at least one support; M<1> = a Group 3, 4, 5 or 6 metal, or a lanthanide or actinide; R<1> = H, a 1-30C carbon-containing group or SiR<3>, or 2 or more R<1> groups with the linking atoms may form an optionally substituted 4-24C ring system; R<3> = H or a 1-40C group; R<2> = a fluorine-containing 1-25C alkyl, 1-25C alkenyl, 6-24C aryl, 7-30C aralkyl or 7-30C alkaryl group; r, n = 1, 2, 3, 4 or 5; m, q = 0, 1, 2, 3 or 4; (q+r) = 5 with v = 0, or 4 with v = 1; (m+n) = 5 with v = 0, or 4 with v = 1; s, t = 1-20; L = halogen or a 1-20C hydrocarbon group; x = 1-4, preferably 2 if M<1> = titanium, zirconium or hafnium; Z = a bridging element; v = 0 or 1. An Independent claim is also included for a process for the production of polypropylene by polymerisation of propylene in presence of this catalyst system.

Description

The present invention relates to a catalyst system comprising metallocenes fluorine-containing substituents, a process for their preparation and their use for the polymerization of propylene.

One of the first reactions in which a metallocene of the fourth subgroup is reacted with fluorine-containing ligands describes the flash pyrolysis of Cp ₂ Ti (C ₆ F ₅ ) ₂ (J. Organomet. Chem. 1963, 1, 98; J. Organomet Chem. 1964, 2, 206). The migration of a fluorine atom occurs. Perfluorinated ligands play an important role in the stabilization of electron-deficient metal centers. For example, the stabilization of cationic metallocenes in Ziegler-Natta polymerization is carried out by perfluorinated tetraphenylborates (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41, 1220).

Stabilizing an electron-deficient metal center is also possible with a partially fluorinated anion in the reaction of dimethyl zirconocene compounds with [PhMe ₂ NH] ⁺ [B (C ₆ H ₄ F) ₄ ] ⁻ (Organometallics 1991, 10, 3910). The coordination of an F atom of the anion to the metal center can be demonstrated using ¹⁹ F NMR spectroscopy.

The reaction of butadiene (zirconocene) with the Lewis acid B (C ₆ F ₅ ) ₃ creates a betaine in which the cationic metal center is stabilized by the coordination of a fluorine atom of the pentafluorophenyl radical (Angew. Chem. 1995, 107, 1867). In this case the coordination is weak so that the labile ligand can be displaced by monomers.

The compounds mentioned so far describe interactions in a more cationic manner Metallocenes with aromatic fluorine-containing ligands. The use of partial  fluorinated or perfluorinated aliphatic substituents Cyclopentadienyl ligands of metallocenes have only been described in isolated cases.

A titanocene is known in which a trifluoromethyl group is attached to one Cyclopentadienyl ligands is bound (JACS 1986, 108, 4228).

An intramolecular coordination of a fluorine atom to the metal center is here hardly possible due to the geometry.

The task now was a catalyst system, the metallocenes with contains fluorine-containing substituents.

The present invention relates to a catalyst system which at least a metallocene with fluorine-containing substituents and at least one Contains cocatalyst component and can optionally be supported, and a Process for its preparation and its use in the polymerization of Propylene.

The catalyst system according to the invention contains

• (a) at least one cocatalyst,
• (b) at least one organometallic compound of the formula (I)
  wherein,
  M ^{1 is} a metal from group 3, 4, 5 or 6 of the periodic table of the elements and also lanthanides or actinides,
  R ^{1 are the} same or different and represent a hydrogen atom, a C ₁ -C ₃₀ carbon-containing group such as C ₁ -C ₂₅ alkyl, e.g. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₂₄ aryl, C ₅ -C ₂₄ heteroaryl such as pyridyl, furyl or quinolyl, C ₇ -C ₃₀ arylalkyl, C ₇ -C ₃₀ alkylaryl, C ₁ -C ₁₂ alkoxy, SiR ³ , in which R ^3, identical or different, represents a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₁₀ fluoroalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₁₀ fluoroaryl, C ₆ - C ₁₀ aryloxy, C ₂ - C ₁₀ alkenyl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl or C ₈ - C ₄₀ arylalkenyl, or two or more radicals R ¹ may be joined together so that the radicals R ¹ and the they connecting atoms of the cyclopentadienyl ring form a C ₄ -C ₂₄ ring system, which in turn can be substituted,
  R ^{2 are the} same or different and are a fluorine-containing C ₁ -C ₂₅ alkyl, fluorine-containing C ₁ -C ₂₅ alkenyl, fluorine-containing C ₆ -C ₂₄ aryl, fluorine-containing C ₇ -C ₃₀ arylalkyl, fluorine-containing C ₇ -C ₃₀ Alkylaryl mean
  r, n are the same or different and are 1, 2, 3, 4 or 5,
  m, q are the same or different and are 0, 1, 2, 3 or 4,
  q + r is 5 for v = 0, and q + r is 4 for v = 1,
  m + n is 5 for v = 0, and m + n is 4 for v = 1,
  s, t are the same or different and are an integer from 1 to 20,
  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 ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₁₄ alkoxy, C ₆ -C ₁₄ aryloxy or C ₆ -C ₄₀ aryl,
  x is an integer from 1 to 4, where M ¹ = Ti, Zr or Hf x is preferably 2,
  Z denotes a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1,
  and if necessary
• (c) at least one carrier.

Particularly preferably, Z is a group M ² R ⁴ R ^5, wherein M ² is carbon, silicon, germanium or tin and R ⁴ and R ^{5 are} identical or different and are a C ₁ - C ₂₀ -hydrocarbon group such as C ₁ -C ₁₀ alkyl or C ₆ -C ₁₄ aryl.

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 , (CH ₃ ) ₂ Si, (CH ₃ CH ₂ ) ₂ Si, (CH ₃ ) ((CH ₃ ) ₃ C) Si, (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , oC ₆ H ₄ or 2,2'- (C ₆ H ₄ ) ₂ .

Z can also form a mono- or polycyclic ring system with one or more radicals R ¹ and / or R ² .

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 C ₁ -C ₂₀ - Carbon-containing groups, such as C ₁ -C ₁₀ alkyl or C ₆ -C ₂₀ aryl, where two or more substituents of the indenyl ring can together form a ring system.

Particularly preferred in formula (I)
M ^{1 is} a metal from group 4 of the periodic table of the elements, such as Ti, Zr or Hf,
R ^{1 are the} same or different and represent a hydrogen atom, a C ₁ -C ₃₀ carbon-containing group such as C ₁ -C ₂₅ alkyl, in particular methyl, ethyl, tert-butyl, cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₂₄ aryl, C ₅ -C ₂₄ heteroaryl such as pyridyl, furyl or quinolyl, C ₇ -C ₃₀ arylalkyl, C ₇ -C ₃₀ alkylaryl, or C ₁ - Is C ₁₂ alkoxy, SiR ³ , in which R ^3, identical or different, represents a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₁₀ fluoroalkyl, C ₁ -C ₁₀ - Alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₁₀ fluoroaryl, C ₆ -C ₁₀ aryloxy, C ₂ -C ₁₀ alkenyl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl or Are C ₈ -C ₄₀ arylalkenyl, or two or more radicals R ¹ can be linked to one another in such a way that the radicals R ¹ and the atoms of the cyclopentadienyl ring connecting them form a C ₄ -C ₂₄ ring system, which in turn can be substituted,
R ^{2 are the} same or different and are a fluorine-containing C ₁ -C ₂₅ alkyl, fluorine-containing C ₁ -C ₂₅ alkenyl, fluorine-containing C ₆ -C ₂₄ aryl, fluorine-containing C ₇ -C ₃₀ arylalkyl, fluorine-containing C ₇ -C ₃₀ - Alkylaryl mean
r, n are the same or different and are 1, 2, 3, 4 or 5,
m, q are the same or different and are 0, 1, 2, 3 or 4,
q + r is 5 for v = 0, and q + r is 4 for v = 1,
m + n is 5 for v = 0, and m + n is 4 for v = 1,
s, t are the same or different and are an integer from 1 to 20,
L are identical or different and represent a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms, in particular C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₁₄ - Aryloxy or C ₆ -C ₄₀ aryl,
x is an integer from 1 to 4, where M ¹ = Ti, Zr or Hf x is preferably 2,
Z denotes a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1.

Examples but not limiting examples of the organometallic compound according to the invention are:
Bis (η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) titanium dichloride
Bis (η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) titanium dichloride
Bis (η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) titanium dichloride
Bis (η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) titanium dichloride
Bis (η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) zirconium dichloride
Bis (η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) zirconium dichloride
Bis (η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) zirconium dichloride
Bis (η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutyl cyclopentadienyl) zirconium dichloride
Bis (η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) hafnium dichloride
Bis (η ⁵ -1'H, 1'H, 2'H, 2, H-perfluorooctylcyclopentadienyl) hafnium dichloride
Bis (η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) hafnium dichloride
Bis (η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) hafnium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) titanium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -cyclopentadienyl) titanium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) (η ⁵ -cyclopentadienyl) titanium dichloride
(η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) (η ⁵ -cyclo pentadienyl) titanium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
(η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) (η ⁵ -cyclo pentadienyl) zirconium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
(η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) (η ⁵ -cyclo pentadienyl) hafnium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -pentamethylcyclopentadienyl) titanium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -pentamethyl cyclopentadienyl) titanium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ pentamethylcyclopentadienyl) zirconium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -pentamethyl cyclopentadienyl) zirconium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -pentamethylcyclopentadienyl) hafnium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -pentamethyl cyclopentadienyl) hafnium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -methylcyclopentadienyl) titanium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -methylcyclopentadienyl) titanium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -methylcyclopentadienyl) zirconium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -methylcyclopentadienyl) zirconium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -methylcyclopentadienyl) hafnium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -methylcyclopentadienyl) hafnium dichloride
Dimethylsilanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) titanium dichloride
Dimethylsilanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-methylcyclopentadienyl) titanium dichloride
Dimethylsilanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3- methylcyclopentadienyl) zirconium dichloride
Dimethylsilanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-methylcyclopentadienyl) zirconium dichloride
Dimethylsilanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3- methylcyclopentadienyl) hafnium dichloride
Dimethylsilanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-methylcyclopentadienyl) hafnium dichloride
Dimethylsilanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) titanium dichloride
Dimethylsilanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ cyclo pentadienyl) titanium dichloride
Dimethylsilanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
Dimethylsilanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
Dimethylsilanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
Dimethylsilanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) hafnium dichloride
1,2 ethanediyl (η ⁵ -3- (2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-methyl cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -3-methyl-cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -butyl cyclopentadienyl) titanium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) zirconium dichloride
1,2-ethanediyl (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) hafnium dichloride
1,2-ethanediyl (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (η ⁵ -3-butyl cyclopentadienyl) hafnium dichloride
Dimethylsilanediylbis (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) titanium dichloride
Dimethylsilanediylbis (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) titanium dichloride
Dimethylsilanediylbis (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -3- (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) hafnium dichloride
Dimethylsilanediylbis (η ⁵ -3- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) hafnium dichloride
(η ⁵ -2 ', 2', 2 ', - trifluoroethyl) cyclopentadienyl) (η ⁵ -butylcyclopentadienyl) titanium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -butylcyclopentadienyl) titanium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) (η ⁵ -butylcyclopentadienyl) titanium dichloride
(η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) (η ⁵ -butyl cyclopentadienyl) titanium dichloride
(η ⁵ -2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -butylcyclopentadienyl) zirconium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -butylcyclopentadienyl) zirconium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) (η ⁵ -butylcyclopentadienyl) zirconium dichloride
(η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) (η ⁵ -butyl cyclopentadienyl) zirconium dichloride
(η ⁵ -2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (η ⁵ -butylcyclopentadienyl) hafnium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (η ⁵ -butylcyclopentadienyl) hafnium dichloride
(η ⁵ -1'H, 1'H, 2'H, 2'H-perfluorohexylcyclopentadienyl) (η ⁵ -butylcyclopentadienyl) hafnium dichloride
(η ⁵ -3 '- (trifluoromethyl) -3', 4 ', 4', 4'-tetrafluorobutylcyclopentadienyl) (η ⁵ -butyl cyclopentadienyl) hafnium dichloride
Dimethylsilanediylbis (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) benzoindenyl) zirconium dichloride
Dimethylsilanediyl bis (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) indenyl) zirconium dichloride
Dimethylsilanediyl bis (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) -4- (1-naphthyl) -indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) -4- (2-naphthyl) -indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) -4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) -4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) -4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (2 ', 2', 2'-trifluoroethyl) -4- (4'-tert-butyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) benzoindenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) -4- (1-naphthyl) indenyl) zirconium dichloride
Dimethylsilanediylbis- (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) -4- (2-naphthyl) indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) -4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl-bis- (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) -4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiy-bis- (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) -4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) -4- (4'-tert-butylphenyl) indenyl) zirconium dichloride

In addition to the dichloride compounds, the dimethyl compounds are also from Meaning.

The compound of formula (I) is prepared by reacting a substituted cyclopentadienide (II) resulting from the reaction of a metallocene with a fluorine and iodine-containing alkyl is obtained, with metal compound (III) and should are exemplified by the following reaction scheme.

In this scheme, 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 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. B. 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) can be isolated or used directly for further reactions. The compound of formula (I) can also be prepared in a one-pot reaction without isolation of intermediate and final stages.

The catalyst system according to the invention contains at least one Metallocene of the formula (I) additionally at least one cocatalyst (component a).

The cocatalyst component contains an aluminoxane, a Lewis acid or one ionic compound, which by reaction with the metallocene this in a cationic compound transferred.

A preferred compound of the general formula (IV) is preferred as the aluminoxane

(R AlO) p (IV)

used. Aluminoxanes can be cyclic as in formula (V)

or linear as in formula (VI)

or of the cluster type as in formula (VII), as described in more recent literature, cf. JACS 117 (1995), 6465-74, Organometallics 13 (1994),

The radicals R in the formulas (V), (VI) and (VII) can be the same or different and a C ₁ -C ₂₀ hydrocarbon group such as a C ₁ -C ₆ alkyl group, a C ₆ - C ₁₈ aryl group, Are benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.

The radicals R are preferably the same and are methyl, isobutyl, n-butyl or phenyl or benzyl, particularly preferably methyl.

If the radicals R are different, they are preferably methyl and hydrogen, Methyl and isobutyl or methyl and n-butyl, where hydrogen or isobutyl or n- Butyl preferably 0.01 to 40% (number of radicals R) are contained.

The production of aluminoxane is carried out according to literature regulations (cf. Polyhedron 9 (1990) 429 and EP-A-302 424).

Regardless of the type of manufacture, all aluminoxane solutions are one changing content of unreacted aluminum starting compound, which in free form or as an adduct, together.

The Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains groups containing C ₁ -C ₂₀ carbon, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as Aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) phenyl.

Examples of Lewis acids are trifluoroborane, tris (4-fluorophenyl) borane, Tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, Tris (pentafluorophenyl) borane, tris (3,5-difluorophenyl) borane and / or tris (3,4,5- trifluorophenyl) borane, di (bis (pentafluorophenyl) boroxy) methylalane, Di (bisphenylboroxy) methylalane, di (bis (pentafluorophenyl) boroxy) isopropylalane.

Compounds which contain a non-coordinating anion, such as tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF ₆ -, CF ₃ SO ₃ - or ClO ₄ - are preferably used as ionic cocatalysts. Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N- are used as the cationic counterion. dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium are used.

Examples of such ionic compounds according to the invention are
Tributylammonium tetra (pentafluorophenyl) borate,
Tributylammonium tetra (pentafluorophenyl) aluminate,
Tributylammonium tetra (trifluoromethylphenyl) borate,
Tributylammonium tetra (4-fluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,
Di (propyl) ammonium tetrakis (pentafluorophenyl) borate,
Di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,
Ferrocenium tetrakis (pentafluorophenyl) borate and / or
Ferrocenium tetrakis (pentafluorophenyl) aluminate.

Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or are preferred N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate.

Mixtures of at least one Lewis acid and at least one can also be used ionic compound can be used.

The catalyst system according to the invention can additionally be a carrier (Component c) included. The carrier can be any organic or be an inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders, such as polyolefins.

Suitable inorganic oxides are, for example, silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures.

The carrier materials used have a specific surface area in the range from 10 m ² / g to 1000 m ² / g, a pore volume in the range from 0.1 ml / g to 5 ml / g and an average particle size from 1 μm to 500 μm. Carriers with a specific surface area in the range from 50 μm to 500 μm, a pore volume in the range between 0.5 ml / g and 3.5 ml / g and an average particle size in the range from 5 μm to 350 μm are preferred. Carriers with a specific surface area in the range from 200 m ² / g to 400 m ² / g, a pore volume in the range between 0.8 ml / g to 3.0 ml / g and an average particle size of 10 μm to 200 are particularly preferred µm.

If the carrier material used is inherently low Moisture content or residual solvent content can cause dehydration or do not dry before use. If not, as with the use of silica gel as a carrier material is dehydration or Drying recommended. The weight loss when glowing (LOI = Loss on ignition) should be 1% or less. Thermal dehydration or Drying of the carrier material can be carried out under vacuum and simultaneously Inert gas blanket such as nitrogen. The drying temperature is in the Range between 100 ° C and 1000 ° C, preferably between 200 ° C and 800 ° C.  

In this case, the pressure parameter is not critical. The duration of the Drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that among the selected Conditions the equilibrium with the hydroxyl groups on the Carrier surface can be done, which is usually between 4 and 8 hours required.

Dehydration or drying of the carrier material is also chemical Possible by placing the adsorbed water and the hydroxyl groups on the Surface are reacted with suitable modifiers. The hydroxyl groups can be reacted with the modifier completely or partially converted into a form that does not lead to any lead to negative interaction with the catalytically active centers. Suitable Modifying agents are, for example, silicon halides and silanes, such as Silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane, amines such as Phenyldimethylamine, pyridine or organometallic compounds of aluminum, Boron and magnesium such as trimethyl aluminum, triethyl aluminum, Triisobutylaluminium, triethylborane, dibutylmagnesium. The chemical Dehydration or modification of the carrier material can take place by that a suspension of the air and moisture Carrier material in a suitable solvent with the modifier in pure form or dissolved in a suitable solvent to react.

Suitable solvents are aliphatic or aromatic hydrocarbons, such as Pentane, hexane, heptane, toluene or xylene. The modification takes place at Temperatures between 25 ° C and 120 ° C, preferably between 50 ° C and 70 ° C. Higher and lower temperatures are possible. The duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours. After this The complete process of chemical dehydration is carried out by the carrier material Filtration isolated under inert conditions, one or more times with suitable inert Solvents as already described have been washed and then dried in an inert gas stream or under vacuum.

Organic carrier materials such as finely divided polyolefin powders, such as polyethylene, Polypropylene, or polystyrene, can and should also be used  before the use of adhering moisture, solvent residues or others Contamination by appropriate cleaning and drying operations be freed.

At least one of the above is used to illustrate the supported catalyst system described metallocene components, at least one cocatalyst component and at least one carrier material in a suitable solvent in any Order contacted. The solvent is removed and the resulting one supported metallocene catalyst system dried to ensure that the Solvent completely or for the most part from the pores of the carrier material Will get removed. The supported catalyst is obtained as a free-flowing powder.

Examples of suitable solvents include alkanes such as pentane, isopentane, hexane, Heptane, octane, and nonane, cycloalkanes such as cyclopentane and cyclohexane, and Aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Most notably toluene is preferred.

The amounts used in the preparation of the supported catalyst system of cocatalyst and metallocene can be varied over a wide range. A molar ratio of cocatalyst to transition metal is preferred Metallocene adjusted from 1: 1 to 1000: 1, very particularly preferably one Ratio from 1: 1 to 400: 1.

The supported catalyst system shown according to the invention can either used directly for the polymerization of propylene or before its use in a polymerization process with one or more olefinic monomers be prepolymerized. Execution of prepolymerization of supported Catalyst systems are described in WO 94/28034.

The additive can be used during or after the preparation of the carrier Catalyst system as a small amount of an α-olefin, such as styrene activity-enhancing component or an antistatic, as in US Serial No. 08/365280 described, are added.  

There is also a process for the production of polypropylene by polymerization of propylene in the presence of the catalyst of the invention. The Polymerization can be a homo- or a copolymerization.

In particular, propylene is homo- or copolymerized.

The polymerization is preferred at a temperature of -60 to 300 ° C, particularly preferably 30 to 250 ° C, carried out. The pressure is 0.5 to 2500 bar, preferably 2 to 1500 bar.

The polymerization can be carried out continuously or batchwise, in one or more stages Solution, in suspension, in the gas phase or in a supercritical medium be performed.

The supported system can again be contaminated as a powder or solvent resuspended and as a suspension in an inert suspension medium in the Polymerization system be metered.

A prepolymerization can be carried out using the catalyst according to the invention. For the prepolymerization, the propylene used in the polymerization is preferred used.

For the production of polypropylene with a broad molecular weight distribution preferably uses catalyst systems that are two or more different Contain metallocenes.

Cleaning is required to remove catalyst poisons present in the propylene with an aluminum alkyl, for example trimethyl aluminum, triethyl aluminum or triisobutyl aluminum advantageous. This cleaning can be done both in Polymerization system itself, or the propylene is added in before brought the polymerization system into contact with the Al compound and then separated again.  

As a molecular weight regulator and / or to increase the activity, if necessary, Hydrogen added. The total pressure in the polymerization system is 0.5 to 2500 bar, preferably 2 to 1500 bar.

The compound according to the invention is used in a concentration, based on the transition metal, of preferably 10 ^-3 to 10 ^-8 , preferably 10 ^-4 to 10 ^-7 mol, transition metal per dm ³ solvent or per dm ³ reactor volume.

Before adding the catalyst system (containing at least one according to the invention Metallocene) can also be another alkyl aluminum compound such as for example trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, Trioctylaluminium or Isoprenylaluminium for inerting the Polymerization system (for example to separate existing Catalyst poisons in propylene) added to the reactor or to the catalyst system become. This is in a concentration of 100 to 0.01 mmol Al per kg Reactor contents added to the polymerization system. To be favoured Triisobutyl aluminum and triethyl aluminum in a concentration of 10 to 01 mmol Al used per kg reactor content. This allows the synthesis of a supported catalyst system, the molar Al / M ratio can be chosen small.

example 1 Synthesis of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) titanium dichloride Synthesis of nickelocene

29.4 g of nickel powder are suspended in 400 ml of dimethoxyethane and 27.3 ml of bromine are added with stirring. The mixture is stirred for 1 hour (h) and the solvent is removed under an oil pump vacuum. The brown residue obtained is taken up in ice-cooling with 400 ml of diethylamine and 98 ml of freshly distilled cyclopentadiene are added. The suspension turns green. After stirring for 12 h at room temperature, solvent residues are removed in an oil pump vacuum and the product is isolated by Soxhlet extraction with 700 ml of petroleum ether.
Yield: 74 g (78%)
Melting point: 173.0 ° C

Synthesis of 2 ', 2', 2'-trifluorocyclopentadiene

6.87 g of nickelocene and 9.51 g of triphenylphosphine are dissolved in 60 ml of diethyl ether and 3.56 ml of 2,2,2-trifluoroethyl iodide are added. The solution turns violet and is stirred for 48 h. The contents of the Schlenk vessel are then condensed into a receiver cooled to -196 ° C. and the diethyl ether is distilled off at a bath temperature of 45 ° C. until the temperature of the distillate is no longer at 35 ° C. and determined using ¹ H NMR the proportion of remaining diethyl ether (1.95 eq).
Yield: 8.95 g (81%).
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.46 (m, 6H, = CH); 3.15 (m, 4H, CH _2); 3.00 (m, 4H, CH ₂ (ring), (The product consists of two double bond isomers)) ppm.
(In addition, the resonances of the contained diethyl ether occur: 3.45 (q); 1.18 (t) ppm).
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -65.7 (t, ³ J _HF = 11.4Hz); -65.9 (t, ³ J _HF = 11.5H4 ppm.

Synthesis of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) titanium dichloride

14.6 mmol of 2 ', 2', 2'-trifluoroethylcyclopentadiene are added in tetrahydrofuran at -78 ° C with 8.8 ml of 1.65M butyllithium solution. At the same time, 0.72 ml of titanium tetrachloride are dissolved in 50 ml of toluene, and 40 ml of tetrahydrofuran are slowly added at -78 ° C. The suspension obtained is added to the above solution at -78 ° C. The mixture is allowed to warm slowly to room temperature, the solvent is removed in an oil pump vacuum and the product is extracted from the residue with methylene chloride.
Yield: 1g (37%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.91 (pt, 4H, RCpH); 5.28 (pt, 4H, RCpH); 3.52 (q, ³ J _FH = 11.0 Hz, 4H, 1'-H) ppm.
¹⁹ F NMR: ([D ₆ ] benzene; 284.1 MHz; 300K): d = -65.17 (s (1H decoupled)); (t, ³ JHF = 11.5Hz) (not decoupled)) ppm.

Example 2 Synthesis of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) zirconium dichloride

11.7 mmol of 2 ', 2', 2'-trifluoroethylcyclopentadiene from Example 1 are mixed in 80 ml of tetrahydrofuran at -78 ° C with 7.1 ml of 1.65M butyllithium solution in hexane. 2.22 g of zirconium tetrachloride-THF adduct, dissolved in 30 ml of tetrahydrofuran, are added to the solution obtained at -78 ° C. The mixture is allowed to warm slowly to room temperature, the solvent is removed in an oil pump vacuum and the product is extracted from the residue with methylene chloride. Yield: 1.89 g (70%)
¹ H-NMR: ([D ₆ ] -benzene; 300.1 MHz; 300 K): d = 5.82 (pt, 4H, RCpH); 5.39 (pt, 4H, RCpH); 3.24 (q, ³ J _FH = 12.5 Hz, 4H, 1'-H) ppm.
¹⁹ F NMR: ([D ₆ ] benzene; 284.1 MHz; 300K): d = -65.14 (s (1H decoupled)); (t, ³ J _HF = 11.5Hz) (not decoupled)) ppm.

Example 3 Synthesis of (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride

1.8 mmol of 2 ', 2', 2'-trifluoroethylcyclopentadiene from Example 1 are added to tetrahydrofuran at -78 ° C with 1.05 ml of 1.65M butyllithium solution. A cooled suspension of 0.46 g of cyclopentadienylzirconium trichloride in 50 ml of tetrahydrofuran is added. The mixture is allowed to warm slowly to room temperature, the solvent is removed in an oil pump vacuum and the product is extracted from the residue with methylene chloride.
Yield: 0.47 g (70%)
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.49 (s, 5H, CpH); 6.38 (m, 4H, RCpH); 3.46 (q, ³ J _FH = 10.8 Hz, 2H, 1'-H) ppm.
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -66.03 (s ( ¹ H-decoupled)); (t, ³ J _HF = 11.5Hz) (not decoupled)) ppm.

Example 4 Synthesis of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) hafnium dichloride

5.18 mmol of 2 ', 2', 2'-trifluoroethylcyclopentadiene from Example 1 are mixed with 3.14 ml of 1.65M butyllithium solution in hexane at -78 ° C. 0.8 g of hafnium tetrachloride is added to the solution obtained at -78 ° C. The mixture is allowed to warm slowly to room temperature, the solvent is removed in an oil pump vacuum and the product is extracted from the residue with methylene chloride. Yield: 1.79 g (64%)
¹ H NMR: ([D ₆ ] -benzene; 300.1 MHz; 300 K): d = 5.73 (pt, 4H, RCpH); 5.31 (pt, 4H, RCpH); 3.24 (q, ³ J _FH = 10.8 Hz, 4H, 1'-H) ppm.
¹⁹ F-NMR: ([D ₆ ] -benzene; 282.4 MHz; 300K): d = -65.8 (s ( ¹ H-decoupled)); (t, ³ J _HF = 11.5Hz) (not decoupled)) ppm.

Example 5 Synthesis of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) titanium dichloride Synthesis of 1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadiene

2.29 g of nickelocene from Example 1 and 3.17 g of triphenylphosphine are dissolved in 5 ml of diethyl ether and mixed with 3.0 ml of 1H, 1H, 2H, 2H-perfluorooctyl iodide. The solution turns violet and is stirred for 48 h. The supernatant solution is then filtered, the precipitate is washed thoroughly and then the solvent is removed. The residue is chromatographed on a short column with pentane and the solvent is removed in an oil pump vacuum.
Yield: 3.67 g (74%)
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.45; 6.39; 6.28; 6.22; 6.05 (each m, 3H, RCpH); 2.97 (pq, (1-isomer), 2.91 (psext, (2-isomer), together 4 H, CH2); 2.67 (m, 4H, 1'-H); 2.31 (m, 4H, 2'-H) ppm.
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -81.24 (m, 3F, 8'-F); -114.77 (m, 2F, 3'-F); -122.07 (m, 2F, 4'-F); -123.06 (m, 2F, 7'-F); -123.67 (m, 2F, 6'-F) -126.37 (m, 2F, 5'F) ppm.

Synthesis of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) titanium dichloride

A solution of 0.75 g of 1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadiene in 40 ml of tetrahydrofuran is mixed with 1.04 ml of 1.65M butyllithium solution at -78 ° C and with a cooled suspension of 0.168 g of titanium tetrachloride-THF adduct in 45 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.
Yield: 0.1 g (12%)
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.39 (pt, 4H, RCpH); 6.28 (pt, 4H, RCpH); 3.12 (m, 4H, 1'-H); 2.48 (m, 4H, 2'-H) ppm.
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -81.0 (m, 6F, 8'-F); -114.3 (m, 4F, 3'-F); -122.1 (m, 4F, 4'-F); -123.1 (m, 4F, 7'-F); -123.6 (m, 4F, 6'-F); -126.3 (m, 4F, 5'-F) ppm.

Example 6 Synthesis of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) zirconium dichloride

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 isolated by extraction with methylene chloride.
Yield: 0.56 g (50%)
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.33 (pt, 4H, RCpH); 6.24 (pt, 4H, RCpH); 2.98 (m, 4H, 1'-H); 2.09 (m, 4H, 2'-H) ppm.
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -81.0 (m, 6F, 8'-F); -114.5 (m, 4F, 3'-F); -122.0 (m, 4F, 4'-F); -123.0 (m, 4F, 7'-F); -123.6 (m, 4F, 6'-F); -126.3 (m, 4F, 5'-F) ppm.

Example 7 Synthesis of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) hafnium dichloride

A solution of 0.87 g of 1'H, 1'H, 2'H, 2'H-PerfIuoroctylcyclopentadien from Example 5 in 60 ml of tetrahydrofuran is mixed at -78 ° C with 1.21 ml of 1.65M butyllithium solution and with a cooled Suspension of 0.305 g of hafnium tetrachloride in 40 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.
Yield: 0.38 g (38%)
¹ H NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.57 (pt, 4H, RCpH); 5.47 (pt, 4H, RCpH); 2.86 (m, 4H, 1'-H); 2.10 (m, 4H, 2'-H) ppm.
¹⁹ F-NMR: ([D ₆ ] -benzene; 282.4 MHz; 300K): d = -81.2 (m, 6F, 8'-F); -114.5 (m, 4F, 3'-F); -121.9 (m, 4F, 4'-F); -122.9 (in, 4F, 7'-F); -123.4 (m, 4F, 6'-F); -126.2 (m, 4F, 5'-F) ppm.

Example 8 Synthesis of ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride

A solution of 1.31 g of 1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadiene from Example 5 in 25 ml of tetrahydrofuran is mixed at -78 ° C with 2 ml of 1.65M butyllithium solution and with a cooled suspension of 1.28 g of cyclopentadienylzirconium trichloride-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 isolated by extraction with methylene chloride and pentane.
Yield: 1.73 g (86%)
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.47 (s, 5H, CpH); 6.32 (pt, 2H, RCpH); 6.23 (pt, 2H, RCpH); 2.98 (m, 2H, 1'H); 2.38 (m, 2H, 2'H) ppm.
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -81.0 (m, 3F, 8'-F); -114.5 (m, 2F, 3'-F); -122.0 (m, 2F, 4'-F); -123.0 (m, 2F, 7'-F); -123.6 (m, 2F, 6'-F); -126.3 (m, 2F, 5'-F) ppm.

Example 9 Synthesis of (1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride

A solution of 1.39 g of 1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadiene from Example 5 in 50 ml of tetrahydrofuran is mixed at -78 ° C with 2.1 ml of 1.65M butyllithium solution and with a cooled suspension of 1.11 g of 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.
Yield: 1.9g (81%)
¹ H NMR: ([D] chloroform; 200.1 MHz; 300 K): d = 6.06 (pt, 2H, RCpH); 5.94 (pt, 2H, RCpH); 3.72 (m, 2H, 1'-H); 2.97 (m, 2H, 2'-H); 2:02 (s, 15H, Cp (CH _{3) 5)} ppm.
¹⁹ F NMR: ([D] chloroform; 282.4 MHz; 300K): d = -80.9 (m, 3F, 8'-F); -114.5 (m, 2F, 3'-F); -122.2 (m, 2F, 4'-F); -123.0 (m, 2F, 7'-F); -123.6 (m, 2F, 6'-F); -126.3 (m, 2F, 5'-F) ppm.

Example 10 Synthesis of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) zirconium dimethyl

To a suspension of 1.05 g of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) zirconium dichloride from Example 2 in 40 ml of diethyl ether, 2.79 ml of 1.68M methyl lithium solution in diethyl ether is slowly added at -78 ° C. The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane. Yield: 0.614 g (73%)
¹ H NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.62 (pt, 4H, RCpH); 5.21 (pt, 4H, RCpH); 2.87 (q, ³ J _FH = 10.6 Hz, 4H, 1'-H); -0.52 (s, 6H, Zr-CH ₃ ) ppm.

Example 11 Synthesis of (2 ', 2', 2'-trifluoroethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl

To a suspension of 0.252 g (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride from Example 3 in 25 ml diethyl ether, 0.8 ml 1.68M methyl lithium solution in diethyl ether is slowly added at -78 ° C . The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane. Yield: 0.162 g (73%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.64 (s, 5H, CpH); 5.63 (pt, 2H, RCpH); 5.27 (pt, 2H, RCpH); 2.87 (q, ³ J _FH = 10.8 Hz, 2H, 1'-H); -0.32 (s, 6H, Zr (CH ₃₎ ppm.

Example 12 Synthesis of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) zirconium dimethyl

To a suspension of 0.51 g of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) titanium dichloride from Example 5 in 50 ml of diethyl ether, 1.04 is slowly added at -78 ° C ml 1.68M methyl lithium solution in diethyl ether. The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane. Yield: 0.302 g (65%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.46 (pt, 4H, RCpH); 5.37 (pt, 4H, RCpH); 2.60 (m, 4H, 1'-H); 2.05 (m, 4H, 2'H); -0.29 (s, 6H, Zr-CH ₃ ) ppm.

Example 13 Synthesis of (1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl

To a suspension of 0.525 g (1'H, 1'H, 2'H, 2'H-perfluorooctyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride from Example 8 in 40 ml diethyl ether, 1.03 ml 1.68 are slowly added at -78 ° C M methyl lithium solution in diethyl ether. The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane. Yield: 0.257 g (55%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.70 (s, 5H, CpH); 5.45 pt, 2H, RCpH); 5.36 (pt, 2H, RCpH); 2.60 (m, 2H, 1'-H); 2.09 (m, 2H, 2'H); -0.21 (s, 6H, Zr- (CH ₃ ) ₂ ) ppm.

Example 14 (1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dimethyl

2.7 ml is slowly added to a suspension of 1.9 g (1'H, 1'H, 2'H, 2'H-perfluorooctylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride from Example 9 in 40 ml diethyl ether at -78 ° C 1.68M methyl lithium solution in diethyl ether. The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane. Yield: 1.33 g (74%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.51 (pt, 2H, RCpH); 5.28 (pt, 2H, RCpH); 2.74 (m, 2H, 1'-H); 2.13 (m, 2H, 2'-H); 1.67 (s, 15H, Cp (CH _{3) 5);} -0.44 (s, 6H, Zr-CH ₃ ) ppm.

Example 15 Synthesis of bis ((2,2 ', 2'-trifluoroethyl) cyclopentadienyl) hafniumdimethyl

To a suspension of 0.5 g bis ((2,2 ', 2', trifluoroethyl) cyclopentadienyl) hafnium dichloride from Example 4 in 50 ml diethyl ether, 1.1 ml 1.68M methyl lithium solution in diethyl ether is slowly added at -78 ° C . The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane.
Yield: 0.358 g (83%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.52 (pt, 4H, RCpH); 5.16 (pt, 4H, RCpH); 2.87 (q, ³ J _FH = 10.7 Hz, 4H, 1'-H); -0.71 (s, 6H, _Hf-CH3) ppm.

Example 16 Synthesis of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) hafnium dimethyl

0.25 ml of 1.68 is slowly added to a suspension of 0.222 g of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) hafnium dichloride from Example 7 in 40 ml of diethyl ether at -78 ° C M methyl lithium solution in diethyl ether. The mixture is allowed to warm to room temperature and the solvent is removed in an oil pump vacuum. The product is isolated by extraction with pentane.
Yield: 0.197 g (91%)
¹ H-NMR: ([D ₆ ] -benzene; 200.1 MHz; 300 K): d = 5.38 (pt, 4H, RCpH); 5.31 (pt, 4H, RCpH); 2.59 (m, 4H, 1'-H); 2.08 (m, 4H, 2'-H); -0.47 (s, 6H, _Hf-CH3) ppm.

Example 17 Polymerization of propene

200 ml of toluene and 19 ml of 10.5% strength methylaluminoxane solution in toluene are placed in a 1 liter glass autoclave. A solution of 1 ml of 10.5% methylaluminoxane solution in toluene and 40 mg of bis ((1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) zirconium dichloride is added. The polymerization temperature is then set from 0 ° C. and 2 bar of propene are pressed in and kept in the course of the polymerization by means of subsequent metering. Polymerization is stopped by adding 20 ml of methanol / 2N hydrochloric acid (1: 1). The polypropylene obtained is filtered off and dried in an oil pump vacuum.
Activity: 33 g / (mmol.bar.h)

Example 18 Polymerization of propene

200 ml of toluene and 19 ml of 10.5% strength methylaluminoxane solution in toluene are placed in a 1 liter glass autoclave. A solution of 1 ml of a 10.5% methylaluminoxane solution in toluene and 15 mg (1'H, 1'H, 2'H, 2'H-perfluorooctyl) cyclopentadienyl) (cyclopentadienyl) zirconium dichloride is added. The polymerization temperature is then set from 0 ° C. and 2 bar of propene are pressed in and kept in the course of the polymerization by means of subsequent metering. Polymerization is stopped by adding 20 ml of methanol / 2N hydrochloric acid (1: 1). The polypropylene obtained is filtered off and dried in an oil pump vacuum.
Activity: 144 g / (mmol.bar.h)

Claims (7)

1. Containing catalyst system

• (a) at least one cocatalyst,
• (b) at least one organometallic compound of the formula (I)
  wherein,
  M ^{1 is} a metal from group 3, 4, 5 or 6 of the periodic table of the elements and also lanthanides or actinides,
  R ^{1 are the} same or different and are a hydrogen atom, a C ₁ -C ₃₀ carbon-containing group, SiR ³ , wherein R ^{3 are} identical or different a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group, or two or more radicals R ¹ can be connected to one another in such a way that the radicals R ¹ and the atoms of the cyclopentadienyl ring which connect them form a C ₄ -C ₂₄ ring system, which in turn can be substituted,
  R ^{2 are the} same or different and are a fluorine-containing C ₁ -C ₂₅ alkyl, fluorine-containing C ₁ -C ₂₅ alkenyl, fluorine-containing C ₆ -C ₂₄ aryl, fluorine-containing C ₇ -C ₃₀ arylalkyl, fluorine-containing C ₇ -C ₃₀ Alkylaryl mean
  r, n are the same or different and are 1, 2, 3, 4 or 5,
  m, q are the same or different and are 0.1, 2, 3 or 4,
  q + r is 5 for v = 0, and q + r is 4 for v = 1,
  m + n is 5 for v = 0, and m + n is 4 for v = 1,
  s, t are the same or different and are an integer from 1 to 20,
  L are identical or different and represent a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms,
  x is an integer from 1 to 4, where M ¹ = Ti, Zr or Hf x is preferably 2,
  Z denotes a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1,
  and if necessary
• (c) at least one carrier.

2. Catalyst system according to claim 1, characterized in that in formula (I)
M ¹ is titanium, zirconium or hafnium,
R ^{1 are the} same or different and are C ₁ -C ₂₅ alkyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₂₄ aryl, C ₅ -C ₂₄ heteroaryl, C ₇ - C ₃₀ arylalkyl, C ₇ -C ₃₀ alkylaryl, C ₁ -C ₁₂ alkoxy, SiR ³ , wherein R ^{3 are} identical or different C ₁ -C ₂₀ alkyl, C ₁ -C ₁₀ fluoroalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₁₀ fluoroaryl, C ₆ - C ₁₀ aryloxy, C ₂ -C ₁₀ alkenyl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ - Are alkylaryl or C ₈ -C ₄₀ arylalkenyl,
L are the same or different and are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₁₄ aryloxy or C ₆ -C ₄₀ aryl. 3. A catalyst system according to claim 1, characterized in that in formula (I)
R ^{1 are the} same or different and are methyl, ethyl, tert-butyl, cyclohexyl, octyl, pyridyl, furyl or quinolyl. 4. A catalyst system according to claim 1, characterized in that in formula (I)
Z is M ² R ⁴ R ⁵ , where M ^{2 is} carbon, silicon, germanium or tin and R ⁴ and R ^{5 are} identical or different to a C ₁ -C ₂₀ hydrocarbon group such as C ₁ - C ₁₀ alkyl or C ₆ -C ₁₄ mean aryl. 5. A catalyst system according to claim 1, characterized in that in formula (I) Z is CH ₂ , CH ₂ CH ₂ , CH (CH ₃ ) CH ₂ , CH (C ₄ H ₉ ) C (CH ₃ ) ₂ , C ( CH ₃ ) ₂ , (CH ₃ ) ₂ Si, (CH ₃ CH ₂ ) ₂ Si, (CH ₃ ) ((CH ₃ ) ₃ C) Si, (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, ( C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , oC ₆ H ₄ or 2.2 '- (C ₆ H ₄ ) ₂ . 6. Process for the production of polypropylene by polymerization of Propylene in the presence of at least one catalyst system according to one of the Claims 1 to 5. 7. Use of a catalyst system according to one of claims 1 to 5 for Manufacture of polypropylene.