DE19817723A1 - Production of polyolefin other than polypropylene - Google Patents

Abstract

Polyolefins other than polypropylene are obtained by polymerisation of olefins in presence of special fluorine-substituted bridged metallocenes and in presence of a mixture of unhalogenated hydrocarbon and halogen-containing hydrocarbon. A process for the production of polyolefins other than polypropylene comprises the polymerisation of olefins in presence of compounds of formula (I) and in presence of a mixture of (A) unhalogenated hydrocarbon(s) and (B) halogen-containing hydrocarbon(s), in which M<1> = a Group 3, 4, 5 or 6 metal, lanthanide or actinide; R<1> = H, a 1-30C fluorine-containing group, SiR<3> or a 1-30C carbon-containing group, or 2 or more R<1> groups with the linking atoms may form an optionally substituted 4-24C ring system, with the proviso that at least one of the R<1> groups carries or is substituted with at least one fluorine atom; R<3> = H or a 1-40C group; q, m = 5 with v = 0, or 4 with v = 1; L = H, 1-10C alkyl or alkoxy, 6-20C aryl, 6-10C aryloxy, 2-10C alkenyl, OH, N(R<12>)2 or halogen; R<12> = 1-10C alkyl or 6-14C aryl; x = 1-4, preferably 2 if M<1> = titanium, zirconium or hafnium; Z = a bridging element; v = 0 or 1 .

Description

The present invention relates to a new process for the production of Polyolefins using specially substituted metallocenes and in Presence of a mixture of special hydrocarbons.

Process for the production of polyolefins using soluble, homogeneous Catalyst systems consisting of a transition metal component of the type a metallocene and a cocatalyst component of the type one Aluminoxane, a Lewis acid or an ionic compound are known. These catalysts deliver polymers and copolymers with narrower activity Molar mass distribution (EP-A0,129,368; EP-A-0,351,392; EP-A-0,416,815).

In conventional polymerization processes with soluble, homogeneous Catalyst systems form heavy deposits on reactor walls and stirrers, if the polymer is obtained as a solid. These deposits always arise from Agglomeration of the polymer particles when metallocene and / or cocatalyst are dissolved are present in the suspension. Such coatings in the reactor systems must be removed regularly, as these quickly reach considerable strengths, a high one Have strength and prevent heat exchange to the cooling medium. Such homogeneous catalyst systems are in the modern polymerization processes in liquid monomer or cannot be used industrially in the gas phase.

To avoid the formation of deposits in the reactor, there are supported catalyst systems have been proposed in which the metallocene and / or as a cocatalyst serving aluminum compound fixed on an inorganic carrier material become.

Metallocenes and corresponding ones are supported from EP-A-0,576,970 Catalyst systems known.  

Macromol. Chem Phys. 1995, 196, 441-446 and J. Appl. Polym. Sci., 1994, 54, 1019-1026 is a special process for polymerization in emulsions Water and oils or organic solvents known in which a Support of the catalyst system is not necessary. This procedure requires in Water-stable starting materials and / or catalysts.

The object of the present invention is a method for the production of polyolefins with specially substituted metallocenes.

The object underlying the present invention is achieved by a Solved polymerization process based on the polymerization with special substituted metallocenes based in a special solvent mixture.

The present invention relates to a process for the preparation of polyolefins by polymerizing olefins, characterized in that the polymerization in the presence of a 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} identical or different and are a hydrogen atom, a C ₁ -C ₃₀ fluorine-containing group, preferably C ₁ -C ₂₄ fluoroalkyl, C ₆ -C ₁₄ fluoroaryl, C ₇ -C ₃₀ fluoroarylalkyl, C ₇ -C ₃₀ - Fluoroalkylaryl or C ₂ -C ₂₅ fluoroalkenyl, SiR ³ , in which R ^3, identical or different, represents a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group, preferably 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 a C ₁ -C ₃₀ carbon-containing group, preferably 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, in particular pyridyl, furyl or quinolyl, or C ₁ -C ₁₂ alkoxy, or two or more R ¹ radicals can be linked to one another in such a way that the R ¹ radicals and the atoms of Cycl opentadienyl ring form a C ₄ -C ₂₄ ring system which in turn can be substituted, with the proviso that at least one of the radicals R1 carries at least one fluorine atom or is substituted with a fluorine atom,
q is 5 for v = 0, and q is 4 for v = 1,
m is 5 for v = 0 and m is 4 for v = 1,
L are the same or different and are a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ -C ₁₀ Alkenyl group, an OH group, an NR ¹² ₂ group, where R ^{12 is} a C ₁ to C ₁₀ alkyl group or C ₆ to C ₁₄ aryl group, or a halogen atom,
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 is contained in the presence of a mixture

• A) at least one non-halogenated hydrocarbon and
• B) at least one halogen-containing hydrocarbon

is carried out, with the exception of the production of polypropylene.

The compound of formula (I) is preferably in the form of a catalyst system before containing at least one specially substituted metallocene, at least one Cocatalyst, and optionally at least one further additive component.

At least one is used as the metallocene component of the catalyst system Compound of formula (I) above used.

Z is preferably a group M ² R ⁴ R ⁵ , in which M ^{2 is} carbon, silicon, germanium or tin and R ⁴ and R ^5, identical or different, are a C ₁ -C ₂₀ hydrocarbon group, preferably 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 .

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 such 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 which can be halogenated, linear, cyclic or branched and / or substituted with C ₁ -C ₂₀ carbon-containing groups, e.g. For example, a C ₁ -C ₁₀ - alkyl group, C ₂ -C ₁₀ -alkenyl, C ₆ -C ₂₀ -aryl group, a C ₇ -C ₄₀ - aralkyl group, a C ₇ -C ₄₀ -alkylaryl group or a C ₈ -C ₄₀ arylalkenyl group, a C ₆ to C ₂₀ aryl group, in particular a phenyl, naphthyl, phenanthryl or anthracenyl group, which is fluorinated and / or perfluorinated C ₁ to C ₁₀ hydrocarbon radicals, in particular CF ₃ or C ₂ F ₅ radicals, mean that two or more substituents of the indenyl ring can together form a ring system.

The 4,5,6,7-tetrahydroindenyl analogs corresponding to the compounds (I) are also important.

In formula (I) it is preferred that
M ¹ denotes titanium, zirconium or hafnium,
R ^{1 are} identical or different and are a hydrogen atom, a C ₁ -C ₃₀ fluorine-containing group, preferably C ₁ -C ₂₄ fluoroalkyl, C ₆ -C ₁₄ fluoroaryl, C ₇ -C ₃₀ fluoroarylalkyl, C ₇ -C ₃₀ - Fluoroalkylaryl or C ₂ -C ₂₅ fluoroalkenyl, SiR ³ , in which R ^3, identical or different, represents a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group, preferably 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 a C ₁ -C ₃₀ carbon-containing group, preferably C ₁ -C ₂₅ alkyl, in particular methyl, ethyl, tert-butyl, cyclohexyl or octyl, C ₂ -C ₂₅ - alkenyl, C ₃ -C ₁₅ alkylalkenyl or C ₆ -C ₂₄ aryl, where two or more radicals R ¹ can be bonded 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 form, which in turn substitute can be, with the proviso that at least one of the radicals R1 carries at least one fluorine atom or is substituted by a fluorine atom,
q is 5 for v = 0, and q is 4 for v = 1,
m is 5 for v = 0 and m is 4 for v = 1,
L are the same or different and are a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ -C ₁₀ alkenyl group, an OH group, an NR ¹² ₂ group, where R ^{12 is} a C ₁ to C ₁₀ alkyl group or C ₆ to C ₁₄ aryl group, or a halogen atom,
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.

Z particularly preferably denotes a group M ² R ⁴ R ⁵ , in which M ^{2 is} carbon, silicon or germanium and R ⁴ and R ^5, identical or different, are a C ₁ -C ₂₀ hydrocarbon group such as C ₁ -C ₁₀ alkyl or C ₆ -C ₁₄ -aryl mean particularly preferably 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, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (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 .

Chiral bridged metallocenes of the formula (I) are particularly preferred, especially those in which v is 1 and one or both cyclopentadienyl rings are substituted such 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 which can be halogenated, linear, cyclic or branched and / or substituted with C ₁ -C ₂₀ -carbon-containing groups, e.g. B. a C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₆ -C ₂₀ aryl group, a C ₇ -C ₄₀ arylalkyl group, a C ₇ -C ₄₀ alkylaryl group or a C ₈ -C ₄₀ - arylalkenyl group, a C ₅ to C ₂₀ aryl group, in particular a phenyl, naphthyl, phenanthryl or anthracenyl group, which is fluorinated and / or perfluorinated C ₁ to C ₁₀ hydrocarbon radicals, in particular 4-fluorophenyl, 3 , 5-difluorophenyl, pentafluorophenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3,5-ditrifluoromethylphenyl, 2,6-ditrifluoromethylphenyl, Pentatrifluormethylphenyl, 4-pentafluoroethylphenyl, 3-pentafluoroethylphenyl, 2-pentafluoroethylphenyl, 3,5-Dipentafluorethylphenyl , 2,6-dipentafluoroethylphenyl, mono-, di-, tri- and tetrafluoronaphthyl, penta (pentatfluoroethyl) phenyl mean, where two or more substituents of the indenyl ring together can form a ring system.

The 4,5,6,7-tetrahydroindenyl analogs corresponding to the compounds (I) are also important.

Examples but not limiting examples of the organometallic compound according to formula (I) 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 (η5-3 '- (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'-tetrafluorobutylcyclopentadienyl) 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
(η5-2 ', 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 -pentamethylcydopentadienyl) 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
(η5-1'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-methyl cyclopentadienyl) 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 cyclopentadienyl) 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-butylcyclopentadienyl) 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-butylcyclopentadienyl) 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-methylcyclopentadienyl) 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-methylcyclopentadienyl) 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-methylcyclopentadienyl) 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 -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-butylcyclopentadienyl) 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
Dimethylsilanediylbis (η ⁵ -2- (2 ', 2', 2 ', - trifluoroethyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (2 ', 2', 2 ', - trifluoroethyl) -4- (1-naphthyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (2 ', 2', 2 ', - trifluoroethyl) -4- (2-naphthyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (2 ', 2', 2 ', - trifluoroethyl) -4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (2 ', 2', 2 ', - trifluoroethyl) -4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiybis (η ⁵ -2- (2 ', 2', 2 ', - trifluoroethyl) -4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediylbis (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
Dimethylsilanediylbis (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
Dimethylsilanediylbis (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) 4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (η ⁵ -2- (1'H, 1'H, 2'H, 2'H-perfluorooctyl) 4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediybis (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
Dimethylsilanediylbis (2-methyl-4- (4-fluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (2,6-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (pentafluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (4-trifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (2,6-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (pentatrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (2,6-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (penta (pentafluoroethyl) phenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-difluorophenyl) -6-phenyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-ditrifluoromethylphenyl) -6-phenyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (4-pentafluoroethylphenyl) -6-phenyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-dipentafluoromethylphenyl) -6-phenyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl4- (pentafluorophenyl) -6-phenyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-ditrifluoromethylphenyl) -6-methyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-methyl-4- (3,5-ditrifluoromethylphenyl) -6-isopropyl-indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isopropyl-4- (3,5-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isopropyl-4- (4-trifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isoprnpyl4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isopropyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isopropyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isopropyl-4- (pentafluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-n-butyl-4- (3,5-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-n-butyl-4- (4-trifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-n-butyl4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-n-butyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-n-butyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-n-butyl-4- (pentafluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-sec.-butyl-4- (3,5-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-sec-butyl-4- (4-trifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-sec-butyl-4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-sec-butyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-sec.-butyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-sec.-butyl-4- (pentafluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-iso-butyl-4- (3,5-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-iso-butyl-4- (4-trifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-iso-butyl-4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-iso-butyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-iso-butyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-isobutyl4- (pentafluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-ethyl-4- (3,5-difluorophenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-ethyl-4- (4-trifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-ethyl-4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-ethyl-4- (4-pentafluoromethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-ethyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl ₂
Dimethylsilanediylbis (2-ethyl-4- (pentafluorophenyl) -indenyl) ZrCl ₂ .

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

Production processes for metallocenes of the formula (I) are generally described in Journal of Organometallic Chem. 288 (1985) 63-67 and in the documents cited therein described.

The compounds of the formula (I) used in the process according to the invention are preferably together with at least one cocatalyst or one Cocatalyst component used.

The cocatalyst component contains at least one compound of the aluminoxane or Lewis acid or ionic compound type, which converts this into a cationic compound by reaction with a metallocene. A compound of the general formula (II) is preferred as the aluminoxane

(R AlO) n (II)

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

or linear as in formula (IV)

or of the cluster type as in formula (V) as described in more recent literature are described, cf. JACS 117 (1995), 6465-74, Organometallics 13 (1994), 2957-2969.

The radicals R in the formulas (II), (III), (IV) and (V) 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, 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 aluminoxane can be prepared in various ways by known methods. According to a known method, an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent, such as toluene. To produce an aluminoxane with different alkyl groups R, two different aluminum trialkyls (AlR ₃ + AlR ' ₃ ) are reacted with water in accordance with the desired composition and reactivity, cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0,302,424.

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.

Organoboron compounds are particularly preferred. Examples of Lewis acids are trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, Tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, Tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, Tris (3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred, Di (bis (pentafluorophenyl) boroxy) methylalan, di (bisphenylboroxy) methylalan, 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 are
Triethylammonium tetra (phenyl) borate, tributylammoniumtetra (phenyl) borate, trimethylammoniumtetra (tolyl) borate, tributylammoniumtetra (tolyl) borate, tributylammonium tetra (pentafluorophenyl) borate, tributylammoniumtetra (pentafluorophenyl) aluminate, tripropylammoniumtetra (dimethylphenyl) borate, tributylammoniumtetra (trifluoromethylphenyl) borate, tributylammoniumtetra ( 4-fluorophenyl) borate, N, N-dimethylanilinium tetra (phenyl) borate, N, N-diethylanilinium tetra (phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) propyl ammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (phenyl) borate, triethylphosphonium tetrakis (phenyl) borate, diphenylphosphonium tetrakis (phenyl) boryl, tri (methyl) (phenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentaf luorophenyl) aluminate, triphenylcarbenium tetrakis (phenyl) aluminate, ferrocenium tetrakis (pentafluorophenyl) borate and / or ferrocenium tetrakis (pentafluorophenyl) aluminate.

Triphenylcarbenium tetrakis (pentafiuorophenyl) 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.

At least one of the above is used to represent the catalyst system described metallocene components (compound of formula I) in one suitable solvents with at least one of those described above Cocatalyst components contacted to form a soluble reaction product to obtain.

Preferred solvents for the preparation of the metallocene-cocatalyst mixture are hydrocarbons and hydrocarbon mixtures used in the selected Reaction temperature are liquid and in which the individual components prefer to solve. However, the solubility of the individual components is not Prerequisite if it is ensured that the reaction product from metallocene and cocatalyst component is soluble in the chosen solvent. 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 catalyst system 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 of 1: 1 to 500: 1. In the case of methylaluminoxane, 30% are preferred toluene solutions used, the use of 10% solutions is but also possible.  

The preactivation time is 1 minute to 200 hours. The pre-activation can take place at room temperature (25 ° C). The application of higher temperatures can shorten the required preactivation time in individual cases and a cause additional activity increase. In this, higher temperature means Case a range between 50 ° C and 100 ° C.

As an additive, during or after the production of the metallocene cocatalyst Blend a small amount of an α-olefin, such as styrene, as an activity enhancer Component or an antistatic, as in US Serial No. 08/365280 described be added.

The present process for the production of polyolefins - excepted Polypropylene - by polymerizing olefins can also be obtained using a supported catalyst system are performed. The preparation of such System is described for example in EP-A-0,576,970.

The term polymerisation is a homopolymerization as well as a Understanding copolymerization, but preferably homopolymerization.

For the purposes of the present invention, polyolefins are polymers based on olefins of the formula R ^α -CH = CH-R ^β , in which R ^α and R ^{β are} identical or different and are a hydrogen atom, a halogen atom, an alkoxy-, hydroxy-, alkylhydroxy- , Aldehyde, carbonyl, carboxylic acid or carboxylic acid ester group or a saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms, in particular 1 to 10 carbon atoms, which is alkoxy, hydroxy, alkylhydroxy, aldehyde or carbonyl , Carboxylic acid or carboxylic acid ester group can be substituted, or R ^α and R ^β form one or more rings with the atoms connecting them, with the exception of propylene.

Examples of such olefins are 1-olefins such as ethene, 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 olefins such as Norbornene, tetracyclododecene or methylnorbornene.  

In addition, mixtures of the above olefins can also be copolymerized become.

The polymerization is carried out at a temperature of -60 ° C to 300 ° C, preferably 50 ° C up to 200 ° C, very particularly preferably 50 ° C to 80 ° C. The pressure is 0.5 bar to 2000 bar, preferably 5 bar to 64 bar.

The polymerization can be continuous or discontinuous, in one or more stages are carried out, the process according to the invention always in the presence a mixture of at least two hydrocarbons, one non-halogenated and a halogenated hydrocarbon. Advantageously the two hydrocarbons are not miscible with each other and form a 2- Phase system, the lower phase being the halogenated hydrocarbon.

Examples of suitable non-halogenated hydrocarbons include straight-chain and branched alkanes, especially those with 3 to 20 Carbon atoms, especially pentane, isopentane, hexane, heptane, octane, and Nonane, cycloalkanes such as cyclopentane and cyclohexane, and substituted and unsubstituted aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene.

Examples of suitable halogenated hydrocarbons include or polyfluorinated alkanes, such as perfluoroheptane and perfluorisohexane, one or multiply fluorinated cycloalkanes such as perfluoro (methylcyclohexane).

A mixture of toluene with perfluoro- (methylcyclohexane) used.

The mixing ratio of the two hydrocarbons is 1: 1 to 100: 1, particularly preferably 1: 1 to 10: 1, particularly preferably 1: 1.  

The above mixture is stirred at a speed of 1 to 10,000 Revolutions per minute mixed.

With the aid of the polymerization process according to the invention, a Prepolymerization take place. For prepolymerization this is preferred in the Polymerization used olefin used.

For the production of polyolefins with a broad molecular weight distribution preferably uses catalyst systems that are two or more different Contain metallocenes according to formula I.

As a molecular weight regulator and / or to increase the activity, if necessary, Hydrogen added.

Before adding the catalyst system (containing at least one organometallic Compound according to formula (I) and at least one cocatalyst component) can in addition another alkyl aluminum compound such as Trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or Isoprenyl aluminum for inerting the polymerization system (e.g. to separate existing catalyst poisons in the olefin) into the reactor 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.

The polyolefin produced by the process according to the invention shows one uniform grain morphology and has no fine grain content. In the There are no deposits or caking on polymerization.

The polyolefin produced by the process according to the invention is in particular for the production of tear-resistant, hard and rigid moldings such as fibers,  Filaments, injection molded parts, foils, plates or large hollow bodies, such as pipes, suitable.

Examples General Information

The production and handling of the organometallic compounds was carried out with the exclusion of air and moisture under an argon protective gas, such as Schlenk technology or glove box. All required solvents were flushed with argon before use and absoluteized using a molecular sieve. The metallocenes used were characterized by ¹ H-NMR, ¹³ C-NMR and ¹⁹ F-NMR spectroscopy.

Determination of solubility and partition coefficient for metallocene dichloride

99 mg of the metallocene dichloride are weighed exactly into a Schlenk flask and mixed with 2 ml of perfluoromethylcyclohexane and 10 min. stirred at room temperature. The suspension obtained is filtered through a frit and the precipitate is carefully weighed out. 72 mg of metallocene dichloride are obtained. 1 ml of the filtrate is removed and the same amount of toluene is added. The two-phase mixture is stirred, a stable emulsion being formed. After switching off the stirrer, the phases separate and are dried separately in an oil pump vacuum. The residues are weighed out and analyzed spectroscopically. No metallocene can be detected in the toluene phase. The fluorine phase gives 12 mg from 0.9 ml.
Precipitation: 72 mg of 99 mg from 2 ml of perfluoromethylcyclohexane
Soluble: 28 mg of 99 mg in 2 ml of perfluoromethylcyclohexane
The solubility is therefore L = 0.014 mol / l
Partition coefficient: From 28 mg metallocene in 2 ml solvent mixture:
Toluene: 0 mg from 0.9 ml
Perfluoromethylcyclohexane: 12 mg from 0.9 ml
The distribution coefficient is therefore a = {c (metallocene) perfluoromethylcyclohexane} / { ^{c (metallocene)} toluene} <= 20

example 1

40 mg of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) - (cyclopentadienyl) zirconium dimethyl are mixed with 39 mg of trityltetrakis (pentafluorophenyl) borate in a Schlenk flask. A mixture of 5 ml of perfluoro (methylcyclohexane), 5 ml of toluene and 0.5 ml of triisobutyl aluminum solution is added. The emulsion obtained is evacuated once with vigorous stirring and then aerated with ethene. The precipitated polymer is located between the lower fluorous phase and the upper toluene phase. The polymerization is stopped by adding 2 ml of methanol / 2N hydrochloric acid (1: 1). The polyethylene obtained is filtered off and dried in an oil pump vacuum.
Yield: 230 mg polyethylene

Example 2

In a Schlenk flask, 32 mg of bis (2 ', 2', 2'-trifluoroethyl) cyclopentadienyl) - (cyclopentadienyl) zirconium dimethyl are mixed with 31 mg of trityltetrakis (pentafluorophenyl) borate. A mixture of 2 ml of perfluoro (methylcyclohexane), 8 ml of toluene and 0.5 ml of triisobutyl aluminum solution is added. The emulsion obtained is evacuated once with vigorous stirring and then aerated with ethene. The precipitated polymer is located between the lower fluorous phase and the upper toluene phase. The polymerization is stopped by adding 2 ml of methanol / 2N hydrochloric acid (1: 1). The polyethylene obtained is filtered off and dried in an oil pump vacuum.
Yield: 120 mg of polyethylene

Example 3

In a Schlenk flask, 21 mg of bis (2 ', 2', 2'- trifluoroethyl) cyclopentadienyl) (cyclopentadienyl) zirconiumdimethyl with 21 mg Trityltetrakis (pentafluorophenyl) borate mixed. Add a mixture of 8 ml perfluoro (methylcyclohexane), 2 ml toluene and 0.5 ml triisobutyl aluminum solution.  

The emulsion obtained is evacuated once with vigorous stirring and then aerated with ethene. The precipitated polymer is located between the lower fluorous phase and the upper toluene phase. The polymerization is stopped by adding 2 ml of methanol / 2N hydrochloric acid (1: 1). The polyethylene obtained is filtered off and dried in an oil pump vacuum.
Yield: 140 mg polyethylene.

Claims (12)

1. A process for the preparation of polyolefins by polymerization of olefins, characterized in that the polymerization in the presence of a compound of 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 a hydrogen atom, a C ₁ -C ₃₀ fluorine-containing group, SiR ³ , wherein R ^{3 are} identical or different a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group, or a C ₁ - C ₃₀ - is 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 connecting them form a C ₄ -C ₂₄ ring system, which in turn can be substituted, with the proviso that at least one of the radicals R1 carries at least one fluorine atom or is substituted by a fluorine atom,
q is 5 for v = 0, and q is 4 for v = 1,
m is 5 for v = 0 and m is 4 for v = 1,
L are the same or different and are a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₁₀ aryloxy group, a C ₂ -C ₁₀ alkenyl group, an OH group, an NR ¹² ₂ group, where R ^{12 is} a C ₁ to C ₁₀ alkyl group or C ₆ to C ₁₄ aryl group, or a halogen atom,
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 is contained in the presence of a mixture

• A) at least one non-halogenated hydrocarbon and
• B) at least one halogen-containing hydrocarbon is carried out,

with the exception of the production of polypropylene. 2. The method according to claim 1, characterized in that in formula (I)
R ^{1 are the} same or different and represent a hydrogen atom, C ₁ -C ₂₄ fluoroalkyl, C ₆ -C ₁₄ fluoroaryl, C ₁ -C ₃₀ fluoroarylalkyl, C ₁ -C ₃₀ fluoroalkylaryl, C ₂ -C ₂₅ fluoroalkenyl, SiR ³ , in which R ^3, identical or different, represents a hydrogen atom or 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 ₁ -C ₄₀ arylalkyl, C ₁ -C ₄₀ alkylaryl or C ₈ -C ₄₀ arylalkenyl, or R ¹ identical or different 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 or C ₁ -C ₁₂ alkoxy, with the proviso , which carries at least one of the radicals R1 at least one fluorine atom or is substituted by a fluorine atom. 3. The method according to claim 1, characterized in that in formula (I)
Z is a group 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 and are a C ₁ -C ₂₀ hydrocarbon group. 4. The method 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 . 5. The method according to claim 1, characterized in that the Polymerization is also carried out in the presence of a cocatalyst. 6. The method according to claim 1, characterized in that the halogenated and the halogenated hydrocarbon are not miscible with each other are and form a 2-phase system, the lower phase of the halogenated Is hydrocarbon. 7. The method according to claim 1, characterized in that the not halogenated hydrocarbons a straight-chain and / or a branched alkane, a cycloalkane, a substituted and / or unsubstituted aromatic or a mixture is the same. 8. The method according to claim 7, characterized in that the not halogenated hydrocarbon pentane, isopentane, hexane, heptane, octane, nonane, Cyclopentane, cyclohexane, benzene, toluene. Ethylbenzene, diethylbenzene or a Mixture of the same is. 9. The method according to claim 1, characterized in that the halogenated Hydrocarbon one or more fluorinated alkane, one or more fluorinated Is cycloalkanes or a mixture thereof. 10. The method according to claim 9, characterized in that the halogenated halogenated hydrocarbon perfluoroheptane, perfluoroisohexane, Perfluoro (methylcyclohexane) or a mixture thereof.   11. The method according to claim 8 and 10, characterized in that a Mixture of toluene with perfluoro (methylcyclohexane) is used. 12. The method according to claim, characterized in that the Mixing ratio of the two hydrocarbons is 1: 1 to 100: 1.