DE10226182A1 - New transition metal compound for catalyst system used for preparation of polyolefin, in particular copolymer of various olefins, e.g. ethylene-propylene copolymers for use in producing hard and stiff shaped bodies, e.g. fibers - Google Patents

Abstract

A transition metal compound is new. A transition metal compound of formula (I) is new. [Image] where [Image] (Ia) : divalent group such as compounds of formulae (I.1), (I.2), and (I.3); (Ib) : divalent group such as compounds of formulae (I.4), (I.5), and (I.6); M1>Ti, Zr, or Hf; R1>, R2>1-20C group; R1>', R2>', R4>, R4>', R5>, R5>', R6>, R6>' : H or 1-20C group; R3>6-18C aryl group or 4-18C heteroaryl group; or fluorinated 6-20C aryl or 7-20C alkylaryl, where the aryl part of the groups may bear 1-18C alkyl, 1-18C alkoxy, 2-10C alkenyl, and/or 3-15C alkylalkenyl groups as substituents; R3>R4>forms a monocyclic or polycyclic ring system, which may in turn be substituted; R3'>H or 1-40C group; R3>'R4'>forms a monocyclic or polycyclic ring system, which may in turn be substituted; R7>bridging structural element between the two indenyl radicals and is from M2>R1>0>R1>1> group; M2>Si, Ge, Sn, or C; R1>0>, R1>1>H or 1-20C hydrocarbon-containing group; R8>, R9>halo, 1-20C alkyl, or optionally substituted phenoxide;and R8>R9>forms a monocyclic or polycyclic ring system, which may in turn be substituted. [Image] Independent claims are also included for: (a) a ligand system of formula (II) or its double bond isomers; (b) a process for preparing ansa-metallocene of (I); (c) a catalyst system comprising (I) and cocatalyst(s), and/or supports; and (d) a process of preparing a polyolefin by polymerization of olefin(s) in the presence of (I). [Image].

Description

The present invention relates to a method for producing Transition metal compounds, especially of ansa-bisindenyl-metallocenes with special Substitution patterns, the corresponding transition metal compounds themselves and their use in Manufacture of catalyst systems and the application of the catalyst systems in the Polymerization and copolymerization of olefins.

Metallocenes, optionally in combination with one or more cocatalysts, used as a catalyst component for the polymerization and copolymerization of olefins become. In particular, halogen-containing metallocenes are used as catalyst precursors, which are converted, for example, by an aluminoxane into a polymerization-active cationic Have the metallocene complex transferred (EP-A-129368).

The production of metallocenes and ansa-metallocenes is known per se (US 4,752,597; US 5,017,714; EP-A-320762; EP-A-416815; EP-A-537 686; EP-A-669 340; H. H. Brintzinger et al .; Angew. Chem., 1995, 107: 1255; H. H. Brintzinger et al., J. Organomet. Chem. 232 (1982), 233). For example, cyclopentadienyl metal compounds with halides of Transition metals such as titanium, zirconium and hafnium are implemented.

EP-A-0 576 970 describes C ₂ -symmetrical metallocenes with aryl-substituted indenyl derivatives as ligands, the process for their preparation and their use as catalysts. According to this patent application, the metallocene catalysts are built up as an intermediate via a 2-alkyl-4-aryl-1-indanone. No 2,3-dialkyl-4-aryl-1-indenes can be prepared directly from these indanones.

EP-A-0 659 757 describes C ₁ -symmetrical metallocenes based on substituted indenyl ligands, the indenyl ligands mentioned there not being substituted at position 3 of the indenyl.

WO 01/48034 describes ansa-bisindenyl-metallocenes with a combination different substituents at positions 2 and 4 on the indenyl ligand. With the available from it Catalyst systems can be used both with propylene-ethylene copolymers and with the rubber phase sufficient molecular weight as well as propylene homopolymers with a sufficiently high melting point for sufficient rigidity of the matrix.

By varying the substitution pattern on the ligand systems of ansa metallocenes the spatial conditions around the active center, as well as its electronic Structure changed. This allows, for example, the polymerization behavior of the Catalyst components, as well as ultimately the properties of the polymers such as isotacticity, Chain length or molecular weight and ultimately the macroscopic material properties of these Affect polymers.

However, especially in the ethylene / propylene copolymerization Catalyst systems of the prior art mentioned mostly copolymers with molar masses that are still too low and / or received too little ethylene incorporation. There is therefore a need for suitable ones Catalyst systems that have particularly high ethylene incorporation rates in the ethylene / propylene Allow copolymerization with high isotacticity of the polypropylene content. There is also a need for catalyst systems that have a high molecular weight and a high Ethylene incorporation rate without a drop in the molecular weight of the copolymer and an increase in the molecular weight of the resulting copolymer in comparison to the molecular weight of the homopolymer. Further there is a continuing need for simple and highly effective synthetic methods multiply substituted indenyl ligand systems for use in polymerization-active Metallocene compounds.

The object was therefore to provide new C ₁ and C ₂ -symmetrical metallocenes as catalysts or catalyst components for olefin polymerization which avoid the disadvantages of the prior art and enable targeted control of the polymerization behavior and the polymer properties.

The solution to the above-mentioned problem consists in the inventive Transition metal compounds according to claim 1, a process for their preparation Transition metal compounds according to the independent process claim and their use as Catalyst component in the (co) polymerization of olefins according to the independent Use claim.

Preferred embodiments result from the combination of the features of independent claims with the features of the respective dependent subclaims.

Transition metal compound

Surprisingly, it was found that metallocenes with a certain Substitution patterns at the 2-, 3- and 4-positions of at least one indenyl radical or spatially corresponding positions of a cyclopentadienyl derivative the above tasks solve particularly well.

According to a first aspect, the present invention thus relates to transition metal compounds of the formula (I)


wherein


for a two-tier group like


especially for


stands and


for a two-tier group like


stands, and in what
M ¹ is titanium, zirconium or hafnium, preferably zirconium;
R ¹ , R ^{2 are} identical or different and represent a C ₁ -C ₂₀ carbon-containing group, such as linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and also fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ arylalkyl;
R ¹ ', R ² ' are the same or different, identical or different from R ¹ or R ² , and are hydrogen or a C ₁ -C ₂₀ carbon-containing group, such as linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ arylalkyl;
R ^{3 is} a C ₁ -C ₄₀ carbon-containing group, such as a C ₆ -C ₁₈ aryl group, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and fluorine-containing C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ arylalkyl, the aryl part of these groups optionally having linear or branched C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₀ -Alkenyl or C ₃ -C ₁₅ -alkylalkenyl can be substituted one or more times, or R ³ forms a mono- or polycyclic ring system with R ⁴ , which in turn can optionally be substituted;
R ³ 'is hydrogen or a C ₁ -C ₄₀ carbon-containing group, such as a C ₆ -C ₁₈ aryl group, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and fluorine-containing C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ arylalkyl, the aryl part of these groups optionally having linear or branched C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₀ Alkenyl or C ₃ -C ₁₅ alkylalkenyl can be mono- or polysubstituted, or R ³ 'with R ⁴ ' forms a mono- or polycyclic ring system which in turn can optionally be substituted;
R ⁴ , R ⁴ 'are identical or different and are hydrogen or a C ₁ -C ₂₀ carbon-containing group, such as linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl ; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ arylalkyl;
R ⁵ , R ⁵ ', R ⁶ , R ⁶ ' are the same or different and are hydrogen or a C ₁ -C ₂₀ carbon-containing group, such as linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₅ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; as well as fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ arylalkyl;
R ^{7 is} a bridging structural element between the two indenyl radicals, selected from the group M ² R ¹⁰ R ¹¹ , in which M ^{2 is} silicon, germanium, tin or carbon, preferably silicon and R ¹⁰ and R ^{11 may be the} same or different and hydrogen or a C ₁ -C ₂₀ hydrocarbon-containing group such as linear or branched C ₁ -C ₁₀ alkyl, C ₆ -C ₁₄ aryl; Trialkylsilyl, in particular trimethylsilyl, triarylsilyl or an alkyl-aryl-silyl group;
R ⁸ , R ^{9 can be the} same or different and represent halogen, linear or branched C ₁ -C ₂₀ alkyl, substituted or unsubstituted phenolate, or R ⁸ and R ⁹ can be linked to one another and form a mono- or polycyclic ring system, which in turn can be optionally substituted.

Compounds of the formula (I) which are those which are particularly preferred


For


stands, and


For


stands, wherein the substituents R ³ to R ⁶ and R ³ 'to R ⁶ ' are as defined above.

Metallocenes of the formula (I) in which R ¹ 'is not hydrogen, R ² ' is hydrogen and R ³ 'is C ₆ -C ₂₀ aryl are particularly preferred.

The substituents are further defined according to the present invention as follows:
The term "alkyl", as used in the present context, includes linear or mono- or optionally also multi-branched saturated hydrocarbons, which can also be cyclic. A C ₁ -C ₁₈ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or is preferred Cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, sec-butyl or tert-butyl.
The term "alkenyl", as used in the present context, includes linear or single or optionally also multi-branched hydrocarbons with at least one, possibly also several CC double bonds, which can be cumulated or alternated.
The term "alkylalkenyl", as used in the present context, includes linear or mono- or optionally also multi-branched hydrocarbons with at least one, possibly also several CC double bonds, which are isolated, so that the substituent has both alkyl and alkenyl segments ,
The term "aryl", as used in the present context, denotes aromatic and optionally also condensed polyaromatic hydrocarbon substituents, optionally with linear or branched C ₁ -C ₁₈ alkyl, C ₁ -C ₁₆ alkoxy, C ₂ -C ₁₀ alkenyl or C. ₃ -C ₁₅ alkylalkenyl can be substituted one or more times. Preferred examples of aryl substituents are in particular phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthracenyl, 3,5-dimethylphenyl, 3, 5-di-tert-butylphenyl or 4-trifluoromethylphenyl.
The term "heteroaryl" as used herein refers to aromatic hydrocarbon substituents in which one or more carbon atoms have been replaced by nitrogen, phosphorus, oxygen or sulfur atoms or combinations thereof. Like the aryl radicals, these can optionally be mono- or polysubstituted with linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl. Preferred examples are pyridinyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyrimidinyl, pyrazinyl and the like, as well as derivatives thereof substituted with methyl, ethyl, propyl, isopropyl and tert-butyl radicals.
The term "arylalkyl", as used here, denotes aryl-containing substituents whose aryl radical is linked to the indenyl radical via an alkyl chain. Preferred examples are benzyl, substituted benzyl, phenethyl, substituted phenethyl and the like.
By "fluorine-containing" it is meant that at least one, preferably several and at most all, hydrogen atoms of a substituent are replaced by fluorine atoms. Examples of preferred fluorine-containing substituents according to the invention are trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorophenyl, 4-trifluoromethylphenyl, 4-perfluoro-tert-butylphenyl and the like.
The term "bridging structural element" denotes a double-bonded group which connects the two indenyl radicals to one another via positions 1 and 1 '. Preferred examples of these are groups with the structure M ² R ¹⁰ R ¹¹ , in which M ^{2 is} silicon and R ¹⁰ and R ^{11 may be the} same or different and a C ₁ -C ₂₀ -hydrocarbon-containing group such as C ₁ -C ₁₀ alkyl, C ₆ -C ₁₄ aryl, trialkylsilyl, in particular trimethylsilyl, triarylsilyl or an alkyl aryl silyl group. Particularly preferred bridging structural elements are Si (Me) ₂ , Si (Ph) ₂ , Si (Me) (Et), Si (Ph) (Me), Si (Ph) (Et), Si (Me) (SiMe ₃ ), Si (Et) ₂ , where Ph is a substituted or unsubstituted phenyl, Me is methyl and Et is ethyl.

According to a preferred embodiment of the present invention there is provided a transition metal compound of the formula (I), in which:
M ¹ is zirconium;
R ¹ , R ^{2 are the} same or different and are a C ₁ -C ₁₂ alkyl group, preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, cyclopentyl or are cyclohexyl, particularly preferably are methyl, ethyl or isopropyl;
R ¹ ', R ² ' are the same or different and are hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, cyclopentyl or cyclohexyl, particularly preferably hydrogen Are methyl, ethyl or iso-propyl, very particularly preferably R ¹ 'being methyl, ethyl or iso-propyl and R ² ' being hydrogen;
R ³ , R ³ 'are the same or different and represent a C ₆ -C ₁₈ aryl group which may optionally be substituted, in particular identical to phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert -Butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthracenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl or 4-trifluoromethylphenyl, or in which two radicals R ³ with R ⁴ and / or R ³ 'with R ⁴ ' can form a mono- or polycyclic ring system which in turn can optionally be substituted, in particular form a substituted or unsubstituted, preferably an unsubstituted 1,4-buta-1,3-dienylene group, and R ³ 'can also be hydrogen can;
R ⁴ , R ⁴ 'are the same or different and are either hydrogen or R ⁴ with R ³ and / or R ⁴ ' with R ³ 'can form a mono- or polycyclic ring system, hydrogen being preferred;
R ⁵ , R ⁵ ', R ⁶ , R ⁶ ' are identical or different and are hydrogen, linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and also fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, or C ₇ -C ₂₀ arylalkyl, hydrogen atom being particularly preferred;
R ^{7 is} a bridging structural element SiR ¹⁰ R ¹¹ and R ¹⁰ and R ^{11 are} identical or different and mean a group containing C ₁ -C ₂₀ hydrocarbons, R ⁷ particularly preferably being equal to Si (Me) ₂ , Si (Ph) ₂ , Si (Et) ₂ , Si (Me) (Ph), Si (Me) (SiMe ₃ ); and
R ⁸ , R ⁹ is chlorine or methyl.

Bridged metallocene compounds of the formula (I) are very particularly preferred, in which:
M ¹ is zirconium;
R ¹ , R ^{2 are the} same or different and are methyl, ethyl or isopropyl;
R ¹ ', R ² ' are the same or different and are hydrogen, methyl, ethyl or isopropyl, wherein preferably R ² 'is hydrogen and in particular R ¹ ' is methyl;
R ³ , R ³ 'are the same or different and a C ₆ -C ₁₈ aryl group which may optionally be substituted, in particular phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl , 4-methoxyphenyl, 1-naphthyl, 9-anthracenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-trifluoromethylphenyl, C ₄ -C ₁₈ heteroaryl, C ₇ - C ₂₀ arylalkyl, C ₇ -C ₂₀ alkylaryl, fluorine-containing C ₆ -C ₁₈ aryl or fluorine-containing C ₇ -C ₂₀ arylalkyl, and two radicals R ³ with R ⁴ and / or R ³ 'with R ⁴ ' are a mono- or polycyclic ring system can form, which in turn can be optionally substituted;
R ⁴ , R ⁴ 'are the same or different and are either hydrogen or form a mono- or polycyclic ring system with R ³ and R ³ ', hydrogen and the 4,5-benzindenyl skeleton formed being particularly preferred;
R ⁵ , R ⁵ ', R ⁶ , R ⁶ ' are the same or different and are hydrogen or a C ₁ -C ₂₀ carbon-containing group, such as linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and also fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, or C ₇ -C ₂₀ arylalkyl, with hydrogen being particularly preferred;
R ⁷ denotes a bridging structural element between the two indenyl radicals, R ⁷ particularly preferably equal to Si (Me) ₂ , Si (Ph) ₂ , Si (Et) ₂ , Si (Me) (Ph), Si (Me) (SiMe ₃ ) is; and
R ⁸ , R ^{9 is} chlorine or methyl.

Nonlimiting examples of very particularly preferred transition metal compounds of the formula (I) are:
Dimethylsilanediyl (2,3-dimethyl-4-phenyl-indenyl) - (2-methyl-4-phenyl-indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4-phenyl-indenyl) - (2-methyl-4- (1-naphthyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4-phenyl-indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4- (1-naphthyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (3 ', 5'-di-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride;
Dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-isopropyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-methyl-3-ethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-methyl-3-ethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-methyl-3-ethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-isopropyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-ethyl-3-methyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-ethyl-3-methyl-4- (4'-tert-butylphenyl) -indenyl) - (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-isopropyl-3-methyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;
Dimethylsilanediyl- (2-isopropyl-3-methyl-4- (4'-tert-butylphenyl) -indenyl) - (2-ethyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride;

The invention further relates to a ligand system of the formula (II) or its double bond isomers,


wherein the variables are as defined in Formula I, including the preferred embodiments.

The metallocenes of the formula (I) are characterized in that they are in Comparison to most known symmetrically or asymmetrically substituted metallocenes in the copolymerization of propylene with other olefins, especially ethylene deliver high molecular weight copolymers. There is also a similar one compared to the homopolymer Molar mass. In particular, there is a high ethylene content in the copolymer and a high one To emphasize polymerization activity in heterogeneous polymerizations.

Instead of the pure chiral bridged racemic or pseudo-racemic metallocene compounds of the formula (I), mixtures of the metallocenes of the formula (I) and the corresponding meso or pseudo-meso metallocenes can also be used for the catalyst preparation in the catalyst preparation.

Illustrative but non-limiting examples of the metallocenes according to the invention are:
Dimethylsilanediyl-indenyl-L-zirconium
Dimethylsilanediyl-4,5-benzindenyl-L-zirconium
Dimethylsilanediyl-4-phenylindenyl-L-zirconium dichloride
Dimethylsilandiyl-4- (4'-tert-butylphenyl) indenyl-L-zirconium dichloride
Dimethylsilandiyl-4- (1'-naphthyl) indenyl-L-zirconium dichloride
Dimethylsilandiyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl-L-zirconium dichloride
Dimethylsilanediyl (2-methylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-4,5-benzindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-4- (4'-trifluoromethylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-propyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-propyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-propyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-4- (4'-trifluoromethylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-butyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-butyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-butyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-cyclopentyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-cyclopentyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-cyclohexyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-cyclohexyl-4- (3 ', 5'-di-tert-butylphenyl) -indenyl) -L-zirconium dichloride
Dimethylsilanediyl (3-methyl-indenyl) zirconium dichloride -L-
Dimethylsilanediyl (3-methyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (3-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (3-methyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethyl-4,5-benzindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2,3-dimethyl-4- (4'-trifluoromethylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-3-ethyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-3-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-3-ethyl-4- (4'-methoxyphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-3-ethyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-3-ethyl-4- (9'-anthracenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-methyl-3-ethyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-3-methyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-3-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-ethyl-3-methyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-3-methyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-3-methyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isopropyl-3-methyl-4- (3 ', 5'-di-tert-butylphenyl) -indenyl) -L-zirconium dichloride
Dimethylsilanediyl (2-isobutyl-3-methyl-4-phenylindenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-3-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-3-methyl-4- (1'-naphthyl) indenyl) zirconium dichloride -L-
Dimethylsilanediyl (2-isobutyl-3-methyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl) zirconium dichloride -L-
where L are the following substructures:
(2,3-dimethyl-4,5-benzindenyl); (2,3-dimethyl-4-phenylindenyl); (2,3-dimethyl-4- (4'-methylphenyl) indenyl); (2,3-dimethyl-4- (4'-tert-butylphenyl) indenyl); (2,3-dimethyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl); (2,3-dimethyl-4- (4'-trifluoromethylphenyl) -indenyl); (2,3-diethylindenyl); (2,3-diethyl-4-phenylindenyl); (2,3-diethyl-4- (4'-tert-butylphenyl) indenyl); (2,3-diethyl-4- (1'-naphthyl) indenyl); (2,3-diethyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl); (2,3-diethyl-4- (4'-trifluoromethylphenyl) -indenyl); (2,3-dipropyl-4-phenylindenyl); (2,3-dipropyl-4- (4'-tert-butylphenyl) indenyl); (2,3-dipropyl-4- (1'-naphthyl) -indenyl); (2,3-dipropyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl); (2-methyl-3-ethylindenyl); (2-methyl-3-ethyl-4-phenylindenyl); (2-methyl-3-ethyl-4- (4 '.- ethylphenyl) indenyl); (2-methyl-3-ethyl-4- (4'-tert-butylphenyl) -indenyl); (2-methyl-3-ethyl-4- (1'-naphthyl) indenyl); (2-methyl-3-ethyl-4- (3 ', 5'-di-tert-butylphenyl) -indenyl); (2-methyl-3-ethyl-4- (4'-trifluoromethylphenyl) -indenyl); (2-methyl-3-isopropylindenyl); (2-methyl-3-isopropyl-4-phenylindenyl); (2-methyl-3-isopropyl-4- (4'-methylphenyl) -indenyl); (2-methyl-3-isopropyl-4- (4'-tert-butylphenyl) indenyl); (2-methyl-3-isopropyl-4- (1'-naphthyl) -indenyl); (2-methyl-3-isopropyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl); (2-ethyl-3-methyl-4-phenylindenyl); (2-ethyl-3-methyl-4- (4'-tert-butylphenyl) indenyl); (2-ethyl-3-methyl-4- (1'-naphthyl) -indenyl); (2-ethyl-3-methyl-4- (3 ', 5'-di-tert-butylphenyl) indenyl);

Also preferred are the corresponding zirconium dimethyl compounds, the corresponding zirconium- ^4- butadiene compounds, and metallocenes of the formula (I) with zirconium fragments as described in WO 00/31090, and the corresponding titanium and hafnium compounds.

Since, in particular, the interaction of the steric effects of the radicals R ¹ , R ² and R ³ together with the radicals R ¹ ', R ² ' and R ³ 'is important for the polymerization properties of the transition metal compounds of the formula (I) according to the invention, the Indenyl base also through a spatially similar structure, in particular heteroatom-containing bi- or polycyclic hydrocarbon base (see WO 98/22486), which may contain, for example, sulfur, nitrogen, oxygen or phosphorus, preferably nitrogen or sulfur, such as. B. an appropriately substituted cyclopenta [2,3-b] thiophene-6-yl or cyclopent [2,3-b] pyrrol-4-yl base body.

respectively.

Non-limiting examples of such heteroatom-containing radicals are 5-methylcyclopenta [2,3-b] thiophene-6-yl, 5-ethylcyclopenta [2,3-b] thiophene-6-yl, 5-isopropylcyclopenta [2,3-b] thiophene-6-yl, 2,3,5-trimethylcyclopenta [2,3-b] thiophene-6-yl, 3,5-dimethylcyclopenta [2,3-b] thiophene-6-yl, 2,5-dimethyl-3-phenyl-cyclopenta [2,3-b] thiophene-6-yl, 2,5- Dimethyl-3- (p-t-butylphenyl) cyclopenta [2,3-b] thiophene-6-yl, 5-isopropyl-2-methyl-3- (p-t- butylphenyl) cyclopenta [2,3-b] thiophene-6-yl, 2,3,5-trimethyl-3- (p-t-butylphenyl) cyclopenta [2,3- b] thiophene-6-yl, 1,5-dimethyl-cyclopent [2,3-b] pyrrol-4-yl, 1,2,3,5-tetramethyl-cyclopent [2,3- b] pyrrol-4-yl, 2,5-dimethyl-1-phenyl-cyclopent [2,3-b] pyrrol-4-yl, 2,5-dimethyl-1- (p-t-butylphenyl) - cyclopent [2,3-b] pyrrol-4-yl, 5-isopropyl-2-methyl-1- (p-t-butylphenyl) cyclopent [2,3-b] pyrrol-4-yl and 2,5,6-trimethyl-1-phenyl-cyclopent [2,3-b] pyrrol-4-yl.

Synthesis of transition metal compounds

Surprisingly, a synthetic route has now been found through which metallocenes are involved a special substitution pattern, which those of the invention solve underlying tasks particularly well. Selected ansa-bisindenyl-metallocenes, in particular those which carry at least one, in particular exactly one, indenyl ligand which is in the Positions 2, 3 and 4 carrying substituents other than hydrogen accomplish these tasks particularly good. According to the invention, it is possible through a certain combination different indenes particularly high ethylene incorporation rates in ethylene-propylene copolymerization to achieve high isotacticity of the polypropylene component at the same time.

In principle, the metallocenes according to the invention are synthesized according to the following simplified scheme:


where X is Cl, Br, I, O-tosyl and all other constituents and substituents as described above for formula (I), III, III ', IV and VI' being the following structures:

• a) Umsetzen eines 1-Indanons der Formel (III) oder (III') mit einer Organometallverbindung M³R² _mHal_n bzw. M³R²'_mHal_n und anschließende Eliminierung zum substituierten Inden der Formel (IV) bzw. (IV'),
  worin die Variablen R¹, R¹', R², R²', R³, R³', R⁴, R⁴', R⁵, R⁵', R⁶ und R⁶' die Bedeutung wie in Formel (I) haben, M³ ein Alkalimetall, Erdalkalimetall, Aluminium oder Titan ist, Hal Halogen bedeutet, m eine ganze Zahl ist und gleich oder größer 1 ist und die Summe von m + n gleich der Wertigkeit von M³ entspricht;
• b) Deprotonieren des substituierten Indens der Formel (IV) bzw. (IV') und anschließendes Umsetzen des deprotonierten Indens mit Verbindungen des Typs R⁷X₂ zu Verbindungen gemäß Formel (V) bzw. (V') oder deren Doppelbindungsisomere,
  
  
  wobei X gleich Cl, Br, I oder O-Tosyl ist und R⁷ die Bedeutung wie in Formel I hat;
• c) Umsetzen der Verbindung gemäß Formel (V) oder (V') mit einem weiteren deprotonierten Inden, welches durch Deprotoniertung von (IV) oder (IV') erhalten wurde, zum Ligandsystem der Formel (II) oder seiner Doppelbindungsisomere,
  
  
  
• d) Deprotonieren des Ligandsystems der Formel (IIa) oder seiner Doppelbindungsisomere und Umsetzen mit Verbindungen des Typs X₂M¹R⁸R⁹ zum ansa-Metallocen der Formel (I), wobei X die Bedeutung wie in Formel (V) hat und M¹, R⁸ und R⁹ die Bedeutungen wie in Formel (I) haben.

According to a further aspect, the invention thus relates to a process for the preparation of ansa metallocenes of the formula (I), comprising the following steps:

• a) reacting a 1-indanone of the formula (III) or (III ') with an organometallic compound M ³ R ² _m Hal _n or M ³ R ² ' _m Hal _n and subsequent elimination to the substituted indene of the formula (IV) or (IV '),
  where the variables R ¹ , R ¹ ', R ² , R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ', R ⁵ , R ⁵ ', R ⁶ and R ⁶ ' have the meaning as in formula ( I) M ^{3 is} an alkali metal, alkaline earth metal, aluminum or titanium, Hal is halogen, m is an integer and is equal to or greater than 1 and the sum of m + n corresponds to the valence of M ³ ;
• b) deprotonation of the substituted indene of the formula (IV) or (IV ') and subsequent reaction of the deprotonated indene with compounds of the type R ⁷ X ₂ to give compounds of the formula (V) or (V') or their double bond isomers,
  
  
  where X is Cl, Br, I or O-tosyl and R ^{7 has} the meaning as in formula I;
• c) reacting the compound of the formula (V) or (V ') with a further deprotonated indene, which was obtained by deprotonating (IV) or (IV'), to form the ligand system of the formula (II) or its double bond isomers,
  
  
  
• d) deprotonation of the ligand system of the formula (IIa) or its double bond isomers and reaction with compounds of the type X ₂ M ¹ R ⁸ R ⁹ to give the ansa metallocene of the formula (I), where X has the meaning as in formula (V) and M ¹ , R ⁸ and R ^{9 have} the meanings as in formula (I).

If, in the process described above, an spatially similar, in particular heteroatom-containing, bicyclic system is used in place of an indene of the formula (IV) or (IV '), in particular instead of an indene of the formula (IV'), such as, for example, a correspondingly substituted cyclopenta [ 2,3-b] thiophene or cyclopent [2,3-b] pyrrole,


respectively.


the corresponding transition metal compounds of the formula (I) are obtained,


wherein


for a two-tier group like


preferred for a divalent substituted 1,4-buta-1,3-dienylene group


can stand and


for a two-tier group like


can stand, and the indices R ³ , R ⁴ , R ⁵ , R ⁶ , R ³ ', R ⁴ ', R ⁵ 'and R ⁶ ' are as defined in formula (I).

The process according to the invention for the preparation of metallocenes of the formula (I) with or without heterocyclic cyclopentadienyl derivatives is preferably carried out in the ligand system with compounds whose substitutions are as follows:
M ¹ is zirconium;
R ¹ , R ² are the same or different and represent a C ₁ -C ₁₂ alkyl group, preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, iso-butyl, cyclopentyl or cyclohexyl , particularly preferably for methyl, ethyl or isopropyl;
R ¹ ', R ² ' are the same or different and stand for hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, cyclopentyl or cyclohexyl, particularly preferably for hydrogen, methyl , Ethyl or isopropyl, very preferably R ¹ 'being methyl, ethyl or isopropyl and R ² ' being hydrogen;
R ³ , R ³ 'are the same or different and stand for a C ₆ -C ₁₈ aryl group which may optionally be substituted, in particular for phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4- tert-butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthracenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl or 4-trifluoromethylphenyl; or two radicals R ³ with R ⁴ and / or R ³ 'with R ⁴ ' can form a mono- or polycyclic ring system which in turn can optionally be substituted, in particular a substituted or unsubstituted, preferably an unsubstituted 1,4-buta-1 , 3-dienylene group and R ³ 'can also be hydrogen;
R ⁴ , R ⁴ 'are identical or different and are either hydrogen or form a mono- or polycyclic ring system with R ³ or R ³ ', with hydrogen being particularly preferred;
R ⁵ , R ⁵ ', R ⁶ , R ⁶ ' are the same or different and are hydrogen or a C ₁ -C ₂₀ carbon-containing group, such as linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and fluorine-containing C ₁ -C ₁₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, or C ₇ -C ₂₀ arylalkyl, with hydrogen being particularly preferred;
R ⁷ denotes a bridging structural element between the two indenyl radicals, R ⁷ particularly preferably equal to Si (Me) ₂ , Si (Ph) ₂ , Si (Et) ₂ , Si (Me) (Ph), Si (Me) (SiMe ₃ ) is; and
R ⁸ , R ⁹ is chlorine or methyl.

The process according to the invention for the preparation of metallocenes of the formula (I) is particularly preferably carried out with compounds whose substitutions are as follows:
M ¹ is zirconium;
R ¹ , R ² are the same or different and stand for methyl, ethyl or isopropyl;
R ¹ ', R ² ' are the same or different and stand for hydrogen, methyl, ethyl or isopropyl, wherein preferably R ² 'is hydrogen and R ¹ ' is in particular methyl;
and all other substituents are as defined above.

The substituted 1-indanones according to the formulas (III) or (III ') are according to the prior art known synthesis methods, for example that described in WO 98/40331 Procedure, easily accessible.

The radicals R ² and R ² 'are added to the carbon atom of the keto group by the process according to the invention by reacting the cyclic ketone using a suitable organometallic compound M ³ R ² _m Hal _n or M ³ R ² ' _m Hal _n , where M ³ is an alkali metal, alkaline earth metal, aluminum or titanium and Hal means halogen, e.g. B. a Grignard, a lithium, a titanium or an aluminum reagent. These organometallic compounds are also easily accessible according to standard regulations of the prior art or can be purchased commercially. The synthesis of corresponding Grignard reagents is e.g. B. in Holm, Torkil, J. Chem. Soc. Perkin Trans. 2, 1981, 464-467, and in March, Advanced Organic Chemistry, 4th edition 1992 and the literature cited therein. The person skilled in the art will select suitable organometallic compounds depending on the specific substitution patterns and reactivities of the indanone compounds to be reacted.

After the reaction with the appropriate organometallic compound M ³ R ² _m Hal _n or M ³ R ² ' _m Hal _n , an elimination reaction takes place with formation of the double bond in the 5-membered ring. This can be induced, for example, by means of a suitable diluted or undiluted acid, e.g. As hydrochloric acid, sulfuric acid, phosphoric acid, or organic acids such as formic acid, acetic acid, citric acid and the like, in most cases about 6 N hydrochloric acid is preferred.

This gives a substituted indene of the formula (IV) or (IV ') which, after deprotonation on the methylene carbon of the 5-membered ring, with a reagent R ⁷ X ₂ , in the simplest case, for example a dialkyldichlorosilane, to give a compound of the formula (V) or (V ') is implemented. Deprotonation is carried out using suitable bases, such as n-butyllithium, tert-butyllithium, methyllithium, potassium hydride, dibutylmagnesium or the like. Corresponding process steps are known in the prior art and are described, for example, in WO 01/48034.

The compounds of the formula (V) or (V ') are then treated with deprotonated (III) or (III') converted to the corresponding ligand system (IIa). According to the invention, ligands are obtained of the formula (IIa), which preferably carry at least one indenyl radical, in the 2-, 3- and 4-position is each substituted with a radical other than hydrogen.

The ligands (IIa) or analogously also (II) obtained in this way are in turn deprotonated and then reacted with compounds of the type X ₂ M ¹ R ⁸ R ⁹ into the corresponding C1 or C2-symmetrical, preferably C1-symmetrical ansa metallocenes Formula (I) transferred. The corresponding procedure for the synthesis of the complexes is known standard methods of the prior art. The corresponding heterocyclic systems are obtained in an analogous manner using the corresponding heteroatom-containing hydrocarbon base bodies, as also described in WO 98/22486 and as stated above.

The method according to the invention is again based on a specific one


and non-limiting embodiment:
Here, a substituted 1-indanone, such as. B. the imaged 7- (4'-t-butylphenyl) -2-methyl-1-indanone, which can be prepared according to WO 98/40331, with an alkylating organometallic compound, such as. B. a Grignard, a lithium, a titanium or an aluminum reagent. After acid-mediated elimination, a 2,3,4-trisubstituted indene is obtained, which is reacted with a silylated indene, which can be prepared according to WO 01/48034, to form the ligand, which can be converted into the complex by standard methods.

The invention also relates to indenes of the formula (IV) or their double bond isomers


wherein the variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning as in formula I.

The metallocenes of the formula (I) according to the invention are highly active catalyst components for olefin homo- and copolymerization. Depending on the substitution pattern of the ligands, the Metallocenes are obtained as a mixture of isomers. The metallocenes are used for the polymerization preferably used diastereomerically pure.

The racemic or pseudo-racemic metallocenes of the formula (I) are preferred used, but it is also useful to use racemic or pseudo-rac-enriched (Pseudo-) rac / (pseudo-) meso mixtures.

The metallocenes of the formula (I) according to the invention are particularly suitable as a constituent of Catalyst systems for the production of polyolefins by polymerizing at least an olefin in the presence of a catalyst which has at least one cocatalyst and at least one contains a metallocene.

cocatalysts

Another object of the present invention is therefore a catalyst system containing at least one metallocene of the formula (I) (component A) as Organo transition metal compound and at least one cocatalyst (component B).

The cocatalyst forms with the metallocene of the formula (I) according to the invention polymerization-active catalyst system, the cocatalyst serving as a cation-forming compound.

Suitable cation-forming compounds (component B) which are capable of reacting with an organic transition metal compound according to the invention this into a cationic Transfer connection are z. B. Compounds of the aluminoxane type, a strong one neutral Lewis acid, an ionic compound with a Lewis acid cation or an ionic Compound with Bronsted acid as a cation. In the case of metallocene complexes as Organo transition metal compound are often called as cation-forming compounds Metallocenium ion-forming compounds.

The compounds described in WO 00/31090, for example, can be used as aluminoxanes. Open-chain or cyclic aluminoxane compounds of the general formulas (VI) or (VII) are particularly suitable.


in which
R ^{21 represents} a C ₁ -C ₄ alkyl group, preferably a methyl or ethyl group and m represents an integer from 5 to 30, preferably 10 to 25.

These oligomeric aluminoxane compounds are usually prepared by Reaction of a solution of trialkyl aluminum with water. As a rule, the ones obtained are oligomeric aluminoxane compounds as mixtures of different lengths, both linear and also cyclic chain molecules, so that m is to be regarded as the mean. The Aluminoxane compounds can also be mixed with other metal alkyls, preferably with aluminum alkyls available.

Furthermore, as component B) instead of the aluminoxane compounds of the general Formulas (VI) or (VII) modified aluminoxanes can also be used, in some of which Hydrocarbon radicals or hydrogen atoms through alkoxy, aryloxy, siloxy or amide radicals are replaced.

It has proven advantageous to use the organic transition metal compound according to the invention and to use the aluminoxane compounds in amounts such that the atomic ratio between aluminum from the aluminoxane compounds and the transition metal from the Organo transition metal compound in the range from 10: 1 to 1000: 1, preferably from 20: 1 to 500: 1 and in particular in the range from 30: 1 to 400: 1.

Compounds of the general formula (VIII) are strong, neutral Lewis acids

M ⁴ X ¹ X ² X ³ (VIII)

preferred in the
M ^{4 represents} an element of the 13th group of the Periodic Table of the Elements, in particular B, Al or Ga, preferably B,
X ¹ , X ² and X ³ for hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C- Atoms in the aryl radical or fluorine, chlorine, bromine or iodine are particularly halogenaryl, preferably pentafluorophenyl.

Further examples of strong, neutral Lewis acids are mentioned in WO 00/31090.

Particularly preferred are compounds of the general formula (VIII) in which X ¹ , X ² and X ^{3 are} identical, preferably tris (pentafluorophenyl) borane.

Strong neutral Lewis acids which are suitable as cation-forming compounds B) are also the reaction products from the reaction of a boronic acid with two equivalents of one Aluminum trialkyls or the reaction products from the reaction of an aluminum trialkyl with two Equivalents of an acid fluorinated, especially perfluorinated carbon compound such as Pentafluorophenol or bis (pentafluorophenyl) borinic acid.

Salt-like compounds of the cation of the general formula (IX) are ionic compounds with Lewis acid cations.

[(Y ^{a +} ) Q ₁ Q ₂ . , .Q _z ] ^{d +} (IX)

suitable in which
Y represents an element of the 1st to 16th group of the Periodic Table of the Elements,
Q ₁ to Q _z for single negatively charged radicals such as C ₁ -C ₂₈ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 C atoms in the aryl and 1 to 28 C -atoms in the alkyl radical, C ₃ -C ₁₀ cycloalkyl, which is optionally substituted with C ₁ - C ₁₀ alkyl groups may be substituted, halogen, C ₁ -C ₂₈ alkoxy, C ₆ -C ₁₅ -aryloxy, silyl or mercaptyl 15
a for integers from 1 to 6 and
z represents integers from 0 to 5,
d corresponds to the difference a - z, but d is greater than or equal to 1.

Carbonium cations, oxonium cations and sulfonium cations as well as are particularly suitable cationic transition metal complexes. In particular, the triphenylmethyl cation Silver cation and the 1,1'-dimethylferrocenyl cation to name. They preferably have non-coordinating counterions, in particular boron compounds such as those in WO 91/09882 be mentioned, preferably tetrakis (pentafluorophenyl) borate.

Salts with non-coordinating anions can also be combined by adding a boron or Aluminum compound, e.g. B. an aluminum alkyl, with a second compound, which by Reaction can link two or more boron or aluminum atoms, e.g. B. water, and one third compound which is an ionizing ionic with the boron or aluminum compound Forms connection, e.g. B. triphenylchloromethane. In addition, a fourth Compound that also reacts with the boron or aluminum compound, e.g. B. pentafluorophenol, to be added.

Ionic compounds with Bronsted acids as cations preferably also have non-coordinating counterions. Protonated amine or Aniline derivatives preferred. Preferred cations are N, N-dimethylanilinium, N, N-dimethylcylohexylammonium and N, N-dimethylbenzylammonium and derivatives of the latter two.

Preferred ionic compounds B) are especially N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-cyclohexylammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate.

Two or more borate anions can also be connected to one another, as in the dianion [(C ₆ F ₅ ) ₂ BC ₆ F ₄ -B (C ₆ F ₅ ) ₂ ] ^2- , or the borate anion can be bridged with a suitable one functional group on a support surface.

Further suitable cation-forming compounds B) are listed in WO 00/31090.

The amount of strong, neutral Lewis acids, ionic compounds with Lewis acid cations or ionic compounds with Bronsted acids as cations is preferably 0.1 to 20 equivalents, preferably 1 to 10 equivalents, based on the invention Metal compound.

Suitable cation-forming compounds B) are also boron-aluminum compounds such as di- [Bis (pentafluorophenylboroxy)] methylalane. Corresponding boron-aluminum compounds are for example disclosed in WO 99/06414.

Mixtures of all of the aforementioned cation-forming compounds B) can also be used become. Preferred mixtures contain aluminoxanes, especially methylaluminoxane, and an ionic compound, especially one that contains the tetrakis (pentafluorophenyl) borate anion contains, and / or a strong neutral Lewis acid, especially tris (pentafluorophenyl) borane.

Both the organic transition metal compound according to the invention and the cation-forming compounds B) are used in a solvent, aromatic Hydrocarbons with 6 to 20 carbon atoms, in particular xylenes and toluene, are preferred.

As a further component C), the catalyst can additionally contain a metal compound of the general formula (X)

M ⁵ (R ²² ) _r (R ²³ ) _s (R ²⁴ ) _t (X)

in the
M ^{5 is} an alkali metal, an alkaline earth metal or a metal from the 13th group of the periodic table, ie boron, aluminum, gallium, indium or thallium,
R ^{22 is} hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl or arylalkyl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
R ²³ and R ^{24 are} hydrogen, halogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl, alkylaryl, arylalkyl or alkoxy each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
r is an integer from 1 to 3
and
s and t are integers from 0 to 2, the sum r + s + t corresponding to the valency of M ⁵ ,
included, wherein component C) is not identical to component B). Mixtures of different metal compounds of the formula (X) can also be used.

Of the metal compounds of the general formula (X), those are preferred in which
M ^{5 means} lithium, magnesium or aluminum and
R ²³ and R ^{24 are} C ₁ -C ₁₀ alkyl.

Particularly preferred metal compounds of the formula (X) are n-butyllithium, n-butyl-n-octyl- magnesium, n-butyl-n-heptyl-magnesium, tri-n-hexyl aluminum, tri-isobutyl aluminum, Triethyl aluminum and trimethyl aluminum and mixtures thereof.

If a metal compound is used as component C), it is preferably present in the catalyst in an amount such that the molar ratio of M ⁵ from formula (X) to transition metal M ¹ from the organo transition metal compound according to the invention is from 800: 1 to 1: 1, in particular from 200: 1 to 2: 1.

A catalyst system containing one according to the invention is particularly preferred Organo transition metal compound (component A) and at least one cocatalyst (component B), which additionally contains a carrier (component D).

To obtain such a supported catalyst system, the unsupported Catalyst system with a support (component D) are implemented. In principle, the order is Combination of component D), the invention Any organic transition metal compound and the cocatalyst. The organic transition metal compound of the invention and the cocatalyst can be fixed independently or simultaneously. After the individual process steps, the solid with suitable inert solvents such as. B. aliphatic or aromatic hydrocarbons can be washed.

As component D) it is preferred to use finely divided carriers, any one can be organic or inorganic, inert solid. In particular, component D) a porous carrier such as talc, a layered silicate, an inorganic oxide or a fine particle Polymer powder (e.g. polyolefin).

Suitable inorganic oxides can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Examples of oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for. B. MgO, ZrO ₂ , TiO ₂ or B ₂ O ₃ . A preferred mixed oxide is, for example, calcined hydrotalcite.

The carrier materials used preferably have a specific surface area in the range from 10 to 1000 m ² / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 μm. Carriers with a specific surface area in the range from 50 to 500 m ² / g, a pore volume in the range from 0.5 to 3.5 ml / g and an average particle size in the range from 5 to 350 μm are preferred. Carriers with a specific surface area in the range from 200 to 400 m ² / g, a pore volume in the range from 0.8 to 3.0 ml / g and an average particle size of 10 to 100 μm are particularly preferred.

The inorganic carrier can undergo thermal treatment e.g. B. to remove adsorbed water. Such a drying treatment is generally carried out at temperatures in the range from 80 to 300.degree. C., preferably from 100 to 200.degree. C., the drying from 100 to 200.degree. C. preferably under vacuum and / or an inert gas blanket (e.g. nitrogen) takes place, or the inorganic carrier can be calcined at temperatures of 200 to 1000 ° C to adjust the desired structure of the solid and / or the desired OH concentration on the surface if necessary. The carrier can also be treated chemically, it being possible to use customary drying agents such as metal alkyls, preferably aluminum alkyls, chlorosilanes or SiCl ₄ , but also methylalumoxane. Appropriate treatment methods are described, for example, in WO 00/31090.

The inorganic carrier material can also be chemically modified. For example, the treatment of silica gel with NH ₄ SiF _{6 leads} to fluorination of the silica gel surface or the treatment of silica gels with silanes which contain groups containing nitrogen, fluorine or sulfur leads to correspondingly modified silica gel surfaces.

Organic carrier materials such as finely divided polyolefin powder (e.g. polyethylene, polypropylene or Polystyrene) can also be used and should preferably also be used before use of adhering moisture, solvent residues or other contaminants appropriate cleaning and drying operations are exempted. It can too functionalized polymer supports, e.g. B. based on polystyrenes, are used on their functional Groups, for example ammonium or hydroxy groups, at least one of the Catalyst components can be fixed.

In a preferred form of representation of the supported catalyst system, at least one of the organic transition metal compounds according to the invention in a suitable Solvent contacted with at least one cocatalyst component B), wherein preferably a soluble reaction product, an adduct or a mixture is obtained.

The preparation thus obtained is then mixed with the dehydrated or inerted carrier material mixed, the solvent removed and the resulting supported Organic transition metal compound catalyst system dried to ensure that the solvent is complete or is largely removed from the pores of the carrier material. The worn one Catalyst is obtained as a free flowing powder. Examples of the technical realization of the above Methods are described in WO 96/00243, WO 98/40419 or WO 00/05277.

Another preferred embodiment is first the cation-forming compound on the To produce carrier component and then this supported cation-forming compound to bring into contact with the organic transition metal compound according to the invention.

• 1. mindestens einer definierten Bor- oder Aluminiumverbindung,
• 2. mindestens einer neutralen Verbindung, die mindestens ein acides Wasserstoffatom besitzt,
• 3. mindestens einem Träger, bevorzugt einem anorganischen oxidischen Träger und optional einer Base, bevorzugt einer organischen stickstoffhaltigen Base, wie zum Beispiel einem Amin, einem Anilinderivat oder einem Stickstoffheterocyclus.

Combinations which are obtained by combining the following components are therefore also important as cocatalyst systems B):

• 1. at least one defined boron or aluminum compound,
• 2. at least one neutral compound which has at least one acidic hydrogen atom,
• 3. at least one carrier, preferably an inorganic oxidic carrier and optionally a base, preferably an organic nitrogenous base, such as an amine, an aniline derivative or a nitrogen heterocycle.

The boron or aluminum compound used in the preparation of these supported cocatalysts are preferably those of the formula XI


wherein
R ^{70 are the} same or different and are hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl , C ₆ -C ₇ -C _{40 20} aryloxy, C - arylalkyl, C ₇ -C ₄₀ -Halogenarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ -haloalkylaryl, or R ⁷⁰ is an OSiR ⁷⁷ ₃ Group where
R ^{77 are the} same or different and are hydrogen, halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl , C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ - aralkyl, C ₇ -C ₄₀ -Halogenarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ -haloalkylaryl, preferably hydrogen, C ₁ -C ₈ - Mean alkyl or C ₇ -C ₂₀ arylalkyl, and
M ⁶ is boron or aluminum, preferably aluminum.

Trimethylaluminum and triethylaluminum are particularly preferred as compounds of the formula XI and to name tri-isobutyl aluminum.

The neutral compounds which have at least one acidic hydrogen atom and can react with compounds of the formula (XI) are preferably compounds of the formulas XII, XIII or XIV,

R ⁷¹ -DH (XII)

(R ⁷¹ ) _3-h -B- (DH) _h (XIII)

HDR ⁷² -DH (XIV)

wherein
R ^71, identical or different, hydrogen, halogen, a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ - Aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalky, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ haloalkylaryl, represents a Si (R ⁷³ ) ₃ group or a CH (SiR ⁷³ ) ₂ group,
wherein
R ^{73 is} a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ -Arylalky, C ₇ -C ₄₀ - Halogenarylalky, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ -haloalkylaryl, and
R ^{72 is} a divalent C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkylene, C ₁ -C ₂₀ haloalkylene, C ₅ -C ₂₀ arylene, C ₆ -C ₂₀ haloarylene, C ₇ -C ₄₀ arylalkylene, C ₇ -C ₄₀ - Halogenarylalkylen, C ₇ -C ₄₀ -alkylarylene, C ₇ -C ₄₀ -Halogenalkylarylen,
D is an element of the 16th group of the Periodic Table of the Elements or an NR ⁷⁴ group, in which R ^{74 is} hydrogen or a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₂₀ alkyl or C ₆ -C ₂₀ aryl , preferably oxygen and
h is 1 or 2.

Suitable compounds of the formula (XII) are water, alcohols, phenol derivatives, Thiophenol derivatives or aniline derivatives, in particular the halogenated and in particular the perfluorinated alcohols and phenols are important. Examples of particularly suitable compounds are pentafluorophenol, 1,1-bis (pentafluorophenyl) methanol or 4-hydroxy-2,2 ', 3,3', 4,4 ', 5,5', 6,6'- nonafluorobiphenyl.

Suitable compounds of the formula (XIII) are boronic acids and boric acids, boric acids with perfluorinated aryl radicals, such as (C ₆ F ₅ ) ₂ BOH, being particularly worth mentioning.

Suitable compounds of the formula (XIV) are dihydroxy compounds in which the divalent carbon-containing group is preferably halogenated and in particular perfluorinated. An example for such a compound is 4,4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl hydrate.

Examples of the combination of compounds of the formula (XI) with compounds of the formula (XII) or (XIV) are trimethylaluminum / pentafluorophenol, trimethylaluminum / 1-bis (pentafluorophenyl) methanol, trimethylaluminum / 4-hydroxy-2,2 ', 3,3 ', 4,4', 5,5 ', 6,6'-nonafluorobiphenyl, triethyl aluminum / pentafluorophenol or triisobutyl aluminum / pentafluorophenol or triethyl aluminum / 4,4'-dihydroxy-2,2', 3,3 ', 5 , 5 ', 6,6'-octafluorobiphenyl hydrate, for example, reaction products of the following type can be formed.

Examples of the reaction products from the reaction of at least one compound of the formula (XI) with at least one compound of the formula (XIII) are:

In principle, the components can be combined as required.

If necessary, the reaction products from the reaction of at least one compound of the formula XI with at least one compound of the formula XII, XIII or XIV and optionally the organic nitrogen base additionally with an organometallic compound of the formula VI, VII, VIII and / or X combined in order to then support the supported cocatalyst system B) form.

In a preferred embodiment, components 1 (formula XI) and 2 (formulas XII, XII or XIV) and components 3 (carrier) and 4 (base) separately and subsequently reacted with one another, the reaction preferably in an inert solution or suspending agent takes place. The supported cocatalyst B) formed can be inert Solvents and suspending agents are freed before using the invention Organo transition metal component and optionally component C) to the catalyst system is implemented.

It is also possible to prepolymerize the catalyst solid first with α-olefins, preferably linear C ₂ -C ₁₀ -1-alkenes and in particular with ethylene or propylene, and then to use the resulting prepolymerized catalyst solid in the actual polymerization. The mass ratio of the catalyst solid used in the prepolymerization to the copolymerized monomer is usually in the range from 1: 0.1 to 1: 200.

Can also be used as an additive during or after the preparation of the supported Catalyst system a small amount of an olefin, preferably an α-olefin, for example Vinylcyclohexane, styrene or phenyldimethylvinylsilane, as a modifying component, an antistatic or a suitable inert compound such as a wax or oil can be added. The molar The ratio of additives to the organic transition metal compound according to the invention is usually from 1: 1000 to 1000: 1, preferably from 1: 5 to 20: 1.

polymerization

The present invention also relates to a process for the production of polyolefins Polymerization, that is homopolymerization or copolymerization, of at least one olefin in Presence of a catalyst system containing at least one of the invention Organic transition metal compounds of the formulas (I).

In general, the catalyst system together with another metal compound C ') general formula (X), which differs from that in the preparation of the Catalyst system used metal compounds C) of formula (X) can distinguish as a component a catalyst system for the polymerization or copolymerization of olefins. The additional metal compound is usually added to the monomer or the suspending agent and is used to purify the monomer from substances that have catalyst activity can affect. It is also possible to add the catalyst system during the polymerization process add one or more further cation-forming compounds B).

The olefins can be functionalized, olefinic unsaturated compounds such as Ester or amide derivatives of acrylic or methacrylic acid, for example acrylates, methacrylates or acrylonitrile, or nonpolar olefinic compounds, including aryl-substituted α-olefins fall.

Olefins of the formula R ^m -CH = CH-R ⁿ are preferably polymerized, in which R ^m and R ^{n are} identical or different and are hydrogen or a carbon-containing radical having 1 to 20 C atoms, in particular 1 to 10 C atoms, and R ^m and R ⁿ together with the atoms connecting them can form one or more rings.

Examples of such olefins are 1-olefins having 2 to 40, preferably 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or 4-methyl-1- pentene or unsubstituted or substituted vinyl aromatic compounds such as styrene and Styrene derivatives, or dienes such as 1,3-butadiene, 1,4-hexadiene, 1,7-octadiene, 5-ethylidene-2-norbornene, Norbornadiene, ethylnorbornadiene or cyclic olefins such as norbornene, tetracyclododecene or Methylnorbomene.

Propylene or ethylene are particularly preferably homopolymerized with the catalyst system according to the invention, or ethylene is C ₃ -C ₈ -α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene and / or 1-octene and / or cyclic olefins such as norbornene and / or dienes having 4 to 20 carbon atoms, such as 1,4-hexadiene, norbornadiene, ethylidene norbornene or ethylnorbornadiene, copolymerized or, particularly preferably, propylene is copolymerized with ethylene and / or 1-butene. Examples of such copolymers are propylene / ethylene, propylene / 1-butene copolymers, ethylene / 1-hexene, ethylene / 1-octene copolymers, ethylene / propylene / ethylidene norbornene or ethylene / propylene / 1,4-hexadiene terpolymers ,

The polymerization can be carried out in bulk, in suspension, in the gas phase or in a known manner a supercritical medium in the usual, used for the polymerization of olefins Reactors are carried out. It can be carried out discontinuously or preferably continuously in one or several stages. There are solution processes, suspension processes, stirred processes Gas phase process or gas phase fluidized bed process into consideration. As a solvent or Suspending agents can be inert hydrocarbons, for example isobutane, or else Monomers themselves can be used.

The polymerizations can be carried out at temperatures in the range of -60 to 300 ° C and pressures in the Range from 0.5 to 3000 bar. Temperatures in the range of 50 are preferred up to 200 ° C, in particular from 60 to 100 ° C, and pressures in the range from 5 to 100 bar in particular from 15 to 70 bar. The average residence times are usually from 0.5 to 5 hours, preferably from 0.5 to 3 hours. As a molecular weight regulator and / or to increase the Activity can be used in the hydrogenation polymerization. Furthermore, also usual additives such as antistatic agents can also be used. For polymerization, this can Catalyst system according to the invention can be used directly, that is, it is pure in that Polymerization system introduced, or it is for better dosing with inert components such as Paraffins, oils or waxes added.

The organic transition metal compounds according to the invention are very particularly suitable Formulas (I) or the catalyst systems containing them for the preparation of propylene-ethylene Copolymer or polypropylene / propylene-ethylene copolymer blends.

Another object of the invention is thus a process for the preparation of propylene Ethylene copolymer or polypropylene / propylene-ethylene copolymer mixtures in the presence a catalyst system as described above.

With the catalyst systems according to the invention, ethylene-propylene copolymers are used extraordinarily high stereo and regional specificity and high ethylene incorporation rates obtained comparatively low ethylene partial pressure. While with conventional metallocenes like z. B. Dimethylsilandiylbis- (2-methyl-4-phenylindenyl) zirconium dichloride up to the ethylene incorporation rate 10% by weight with the catalysts according to the invention are installation rates of 10-20% by weight.

The copolymer obtained with the catalyst systems according to the invention draws at the same time by a high ethylene content with a high isotacticity of Polypropylene content.

The polymers produced by the process according to the invention are for production Tear-resistant, hard and rigid molded bodies such as fibers, filaments, injection molded parts, foils, sheets or Large hollow bodies (e.g. pipes) are suitable. The molded parts are characterized in particular by a high toughness, even at temperatures below 20 ° C, combined with high rigidity. The invention is illustrated by the following examples which, however, do not restrict the invention.

Examples General Information

The production and handling of organometallic compounds was carried out in the absence of air and moisture under an argon protective gas (Schienk technology or Glove box). All required solvents were flushed with argon before use and over Mol sieve absolute. Substituted 1-indanones were prepared analogously to WO 98/40331. The The synthesis of the dimethylchlorosilyl-substituted indenes was carried out as in DE 199 36 185 or analogously to the regulation described there.

example 1 7- (4'-tert-butylphenyl) -1,2-dimethyl-1-indene

In a 250 ml three-necked flask, 6.1 g (250 mmol) of magnesium shavings were overlaid with 10 ml of diethyl ether and 1 ml of methyl iodide was added. As soon as the reaction started, the remaining 14.6 ml of methyl iodide (250 mmol in total) in 50 ml of diethyl ether were added so that the solution boiled gently. After the addition had ended, the mixture was stirred under reflux for a further 30 min. A solution of 13.9 g (50 mmol) of 7- (4'-tert-butylphenyl) -2-methyl-1-indanone in 60 ml of diethyl ether was then added dropwise at 0 ° C. in the course of 30 min. The mixture was stirred for a further 1 h at 0 ° C. and for 15 min at room temperature and then ice was carefully added at room temperature. 100 ml of 6N HCl were then added dropwise at room temperature. After complete conversion (TLC control), 100 ml of water and 100 ml of diethyl ether were added. The phases were separated and the aqueous phase was extracted three times with 50 ml of diethyl ether each time. The combined organic phases were dried over magnesium sulfate and the solvent was removed in vacuo. The red oil (13.6 g) thus obtained was recrystallized from 75 ml of ethanol. 7- (4'-tert-Butylphenyl) -1,2-dimethyl-1-indene was obtained in a yield of 10.1 g (36.5 mmol / 73%) and in a purity of 99% (GC).
¹ H-NMR (400 MHz, CDCl ₃ ): 7.50-7.20 (m, 7H, aromatic H), 3.41 (s, 2H, benzyl. H), 2.13 (s, 3H, Methyl), 1.61 (s, 3H, methyl), 1.49 (s, 9H, tert-butyl) ppm.

Example 2 Preparation of dimethylsilanediyl-bis- (2,3-dimethyl-4- (4'-tert-butylphenyl) -1-indene)

To 5.52 g (20 mmol) of 7- (4'-tert-butylphenyl) -2,3-dimethyl-1-indene in 40 ml of toluene / 5 ml of THF were added to 8.8 ml at 0 ° C. in the course of 20 min n-BuLi (22 mmol, 2.5 M in toluene) was added dropwise. The mixture was stirred at 0 ° C. for 10 min and at 80 ° C. for 1 h. After cooling to room temperature, the red solution was added at 0 ° C. to a solution of 1.29 g (10 mmol) of dimethyldichlorosilane in 5 ml of toluene. The solution was stirred at 0 ° C. for a further 10 min and then at 75 ° C. for 2 h. The yellow suspension was added to 30 ml of water. The aqueous phase was extracted three times with 30 ml of toluene. The combined organic phases were dried over magnesium sulfate and the solvent was removed in vacuo. The brown oil thus obtained (7.4 g) was purified by flash chromatography on silica gel (mobile phase: dichloromethane / heptane 1: 9, then 1: 4). Dimethylsilanediylbis (2,3-dimethyl-4- (4'-tert-butylphenyl) -1-indene) was obtained in a yield of 3.17 g (5.2 mmol / 52%) and in a purity of 95 % (GC) obtained in the form of a yellow oil. ¹ H NMR (400 MHz, CDCl ₃ ): 7.51-6.89 (m, 14H, aromatic H), 3.72, 3.68 (2 × s, 2H), 2.19, 2, 13 (2 × s, 6H, methyl), 1.59 (s, 6H, methyl), 1.38 (s, 18H, tert-butyl), 0.01, -0.06, -0.19, - 0.31, -0.39 (5 x s, 6H, SiMe ₂ ) ppm.

Example 3 Preparation of dimethylsilanediylbis- (2,3-dimethyl-4- (4'-tert-butylphenyl) - indenyl) zirconium dichloride

To a solution of 850 mg (1.4 mmol) dimethylsilanediyl-bis- (2,3-dimethyl-4- (4-fert-butylphenyl) - 1-indene) in 5 ml of diethyl ether were added at 0 ° C. in the course of 5 min

1.16 ml (2.9 mmol, 2.5 M in toluene) n-BuLi was added dropwise. The red solution was stirred for 13 h at room temperature. Then 326 mg (1.4 mmol) of zirconium tetrachloride were added at 0 ° C. The mixture was stirred at room temperature for a further 2 h. The precipitated orange solid was isolated by filtration through a G3 frit, washed twice with 5 ml of diethyl ether and twice with 5 ml of tetrahydrofuran. After drying in an oil pump vacuum, the complex was obtained in the form of an orange powder with a yield of 494 mg (0.64 mmol / 46%) and in a purity of> 95% (NMR). ¹ H-NMR (400 MHz, CDCl ₃ ): Rac: 7.81-6.69 (m, 14H, aromatic H), 2.00 (s, 6H, methyl), 1.70 (s, 6H, Methyl), 1.36-1.30 (m, 24H, tert-butyl, SiMe ₂ ) ppm.
Meso: 7.81-6.72 (m, 14H, aromatic H), 2.05 (s, 6H, methyl), 1.78 (s, 6H, methyl), 1.36-1.30 (m , 24H, tert-butyl, SiMe ₂ ) ppm.

Example 4 Preparation of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) indene)

To 25.0 g (90.5 mmol) of 7- (4'-tert-butylphenyl) -2,3-dimethyl-1-indene in 250 ml of toluene / 25 ml of THF became 38.0 ml at room temperature within 20 min n-BuLi (95 mmol, 2.5 M in toluene) was added dropwise. The mixture was stirred at 80 ° C. for a further 2 h, during which the resulting Li salt precipitated out. After cooling to room temperature, 32.1 g (90.45 mmol) of 2-methyl-4- (4'-tert-butylphenyl) -1-dimethylchlorosilyl indene were added. After stirring for three hours at 60 ° C., no starting material was detectable by thin layer chromatography. The solution was added to 250 ml of water. After extraction three times with 100 ml of toluene, the combined organic phases were dried over magnesium sulfate. The solvent was removed in vacuo. After drying in an oil pump vacuum, the product was obtained as a yellow, glassy residue with a yield of 53.9 g (quantitative). ¹ H-NMR (400 MHz, CDCl ₃ ): 7.54-7.03 (m, 14H, aromatic H), 6.83 (s, 1H, C = CH), 3.75-3.28, 2.34-1.95, 1.56-1.48 (3 × m, 11H, CH ₃ , benzyl. H), 1.38, 1.37 (2 × s, 18H, tert-butyl), - 0.21, -0.23, -0.25, -0.28 (4 x s, 6H, SiMe ₂ ) ppm.

Example 5 Preparation of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride

To a solution of 53.9 g (90.5 mmol) of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) indenyl) - (2-methyl-4- (4'-tert- butylphenyl) -inden) in 540 ml of diethyl ether, 72.5 ml (181 mmol, 2.5 M in toluene) of n-BuLi were added dropwise at room temperature in the course of 15 min. The red solution was stirred at room temperature for 12 h. Then 22.2 g (95.1 mmol) of zirconium tetrachloride were added at 0 ° C. The mixture was stirred at room temperature for a further 2 h. The precipitated orange solid was isolated by filtration through a G3 frit, washed twice with 100 ml of diethyl ether and twice with 200 ml of tetrahydrofuran. After drying in an oil pump vacuum, the complex was obtained in the form of an orange powder with a yield of 34.8 g (46.1 mmol / 51%) and in a purity of> 95% (NMR). ¹ H-NMR (400 MHz, CDCl ₃ ): pseudo-rac: 7.67-6.99 (m, 14H, aromatic H), 6.97 (s, 1H, C = CH), 2.25, 1.97, 1.67 (3 × s, 9H, CH ₃ ), 1.34 (s, 9H, tert-butyl), 1.33 (s, 6H, SiMe ₂ ) 1.31 (s, 9H, tert-butyl) ppm. Pseudo-meso: 7.69-6.87 (m, 14H, aromatic H), 6.76 (s, 1H, C = CH), 2.31, 2.15, 1.74 (3 × s, 9H, CH ₃ ), 1.48 (s, 3H, SiMe), 1.34, 1.31 (2 × s, 18H, tert-butyl), 1.22 (s, 3H, SiMe) ppm.

Example 6 Preparation of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-isopropyl-4- (4'-tert-butylphenyl) indene)

To 5.0 g (18.1 mmol) of 7- (4'-tert-butylphenyl) -2,3-dimethyl-1-indene in 50 ml of toluene / 5 ml of THF was added to 7.6 ml at room temperature within 20 min n-BuLi (19.0 mmol, 2.5 M in toluene) was added dropwise. The mixture was stirred at 80 ° C. for a further 2 h, during which the Li salt formed precipitated out. After cooling to room temperature, 6.93 g (18.1 mmol) of 2-isopropyl-4- (4'-tert-butylphenyl) -1-dimethylchlorosilyl indene were added. After stirring for three hours at 60 ° C., no starting material was detectable by thin layer chromatography. The solution was added to 50 ml of water. After extraction three times with 50 ml of toluene, the combined organic phases were dried over magnesium sulfate. The solvent was removed in vacuo. After drying in an oil pump vacuum, the product was obtained as a yellow, glassy residue with a yield of 11.67 g (quantitative). ¹ H NMR (400 MHz, CDCl ₃ ): 7.49-7.07 (m, 14H, aromatic H), 6.82 (s, 1H, C = CH), 3.91-1.45 ( m, 9H, CH ₃ , benzyl. H, iso-propyl-H), 1.37, 1.36 (2 X s, 18H, tert-butyl), 1.27-1.05 (m, 6H, iso -Propyl-CH ₃ ), -0.19, -0.25, -0.27, -0.32 (4 x s, 6H, SiMe ₂ ) ppm.

Example 7 Preparation of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-isopropyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride

To a solution of 11.6 g (18.7 mmol) of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) indenyl) - (2-isopropyl-4- (4'-tert- butylphenyl) -inden) in 120 ml of diethyl ether, 14.9 ml (37.3 mmol, 2.5 M in toluene) of n-BuLi were added dropwise at room temperature in the course of 15 min. The red solution was stirred at room temperature for 12 h. Then 4.6 g (19.6 mmol) of zirconium tetrachloride were added at 0 ° C. The mixture was stirred at room temperature for a further 2 h. The precipitated orange solid was isolated by filtration through a G3 frit, washed twice with 30 ml of diethyl ether and once with 50 ml of tetrahydrofuran. After drying in an oil pump vacuum, the complex was obtained in the form of an orange powder with a yield of 5.6 g (7.2 mmol / 38%) and in a purity of> 95% (NMR). ¹ H-NMR (400 MHz, CDCl ₃ ): pseudo-rac: 7.70-6.84 (m, 14H, aromatic H), 6.78 (s, 1H, C = CH), 3.04 ( q, 1H, iso-propyl-CH), 1.99, 1.69 (2 × s, 6H, CH ₃ ), 1.34 (s, 9H, tert-butyl), 1.32 (s, 6H, SiMe ₂ ) 1.31 (s, 9H, tert-butyl), 1.01 (d, 6H, iso-propyl-CH ₃ ) ppm. Pseudo-meso: 7.69-6.88 (m, 14H, aromatic H), 6.75 (s, 1H, C = CH), 3.33 (q, 1H, iso-propyl-CH), 2nd , 07, 1.75 (2 x s, 6H, CH ₃ ), 1.51 (s, 3H, SiMe), 1.35, 1.30 (2 x s, 18H, tert-butyl), 1.24 (s, 3H, SiMe), 1.15 (d, 6H, iso-propyl-CH ₃ ) ppm.

Example 8 7- (4'-tert-butylphenyl) -1-methyl-2-isopropyl-1-indene

In a 250 ml three-necked flask, 6.0 g (245 mmol) of magnesium shavings were overlaid with 10 ml of diethyl ether and 1 ml of methyl iodide was added. As soon as the reaction started, the remaining 14.2 ml of methyl iodide (245 mmol in total) in 50 ml of diethyl ether were added so that the solution boiled gently. After the addition had ended, the mixture was stirred under reflux for a further 30 min. A solution of 13.9 g (49 mmol) of 7- (4'-tert-butylphenyl) -2-isopropyl-1-indanone in 60 ml of diethyl ether was then added dropwise at 0 ° C. in the course of 30 minutes. The mixture was stirred for a further 1 h at 0 ° C. and for 15 min at room temperature and then ice was carefully added at room temperature. 108 ml of 6N HCl were then added dropwise at room temperature. After complete conversion (TLC control), 100 ml of water and 100 ml of diethyl ether were added. The phases were separated and the aqueous phase was extracted three times with 50 ml of diethyl ether each time. The combined organic phases were dried over magnesium sulfate and the solvent was removed in vacuo. The red oil (quant.) Thus obtained was recrystallized from 75 ml of ethanol. 7- (4'-tert-Butylphenyl) -1-methyl-2-isopropyl-1-indene was obtained in a yield of 7.6 g (25 mmol / 51%) and in a purity of 96% (GC). ¹ H-NMR (400 MHz, CDCl ₃ ): 7.45-7.08 (m, 7H, aromatic H), 3.31 (s, 2H, benzyl. H), 2.99 (q, 1H, isopropyl-CH), 1.51 (s, 3H, methyl), 1.37 (s, 9H, tert-butyl), 1.12 (d, 6H, isopropyl-CH ₃ ) ppm.

Example 9 Preparation of dimethylsilanediyl- (2-isopropyl-3-methyl-4- (4'-tert-butylphenyl) - indenyl) - (2-methyl-4- (4'-tert-butylphenyl) indene)

7.6 g (25.0 mmol) of 7- (4'-tert-butylphenyl) -1-methyl-2-isopropyl-1-indene in 80 ml of toluene / 8 ml of THF were added at room temperature in the course of 20 min. 5 ml of n-BuLi (26.3 mmol, 2.5 M in toluene) were added dropwise. The mixture was stirred at 80 ° C. for a further 2 h, during which the resulting Li salt precipitated out. After cooling to room temperature, 8.9 g (25.0 mmol) of 2-methyl-4- (4'-tert-butylphenyl) -1-dimethylchlorosilyl indene were added. After stirring for three hours at 60 ° C., no starting material was detectable by thin layer chromatography. The solution was added to 50 ml of water. After extraction three times with 50 ml of toluene, the combined organic phases were dried over magnesium sulfate. The solvent was removed in vacuo. After drying in an oil pump vacuum, the product was obtained as a yellow, glass-like residue with a yield of 15.6 g (quantitative). ¹ H NMR (400 MHz, CDCl ₃ ): 7.51-7.09 (m, 14H, aromatic H), 6.76 (s, 1H, C = CH), 3.88-1.47 ( m, 9H, CH ₃ , benzyl. H, iso-propyl-H), 1.38, 1.35 (2 X s, 18H, tert-butyl), 1.29-1.04 (m, 6H, iso -Propyl-CH ₃ ), -0.20, -0.25, -0.28, -0.33 (4 x s, 6H, SiMe ₂ ) ppm.

Example 10 Preparation of dimethylsilanediyl- (2-isopropyl-3-methyl-4- (4'-tert-butylphenyl) - indenyl) - (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium dichloride

To a solution of 15.6 g (25.0 mmol) of dimethylsilanediyl- (2-isopropyl-3-methyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'- tert-butylphenyl) -inden) in 125 ml of diethyl ether, 10.5 ml (26.3 mmol, 2.5 M in toluene) of n-BuLi were added dropwise at room temperature in the course of 15 min. The red solution was stirred at room temperature for 12 h. Then 5.8 g (25.0 mmol) of zirconium tetrachloride were added at 0 ° C. The mixture was stirred at room temperature for a further 2 h. The precipitated orange solid was isolated by filtration through a G3 frit, washed twice with 30 ml of diethyl ether and once with 50 ml of tetrahydrofuran. After drying in an oil pump vacuum, the complex was obtained in the form of an orange powder with a yield of 9.2 g (11.7 mmol / 47%) and in a purity of> 95% (NMR). ¹ H NMR (400 MHz, CDCl ₃ ): pseudo-rac: 7.73-6.81 (m, 14H, aromatic H), 6.79 (s, 1H, C = CH), 3.07 ( q, 1H, iso-propyl-CH), 2.01, 1.71 (2 X s, 6H, CH ₃ ), 1.35 (s, 9H, tert-butyl), 1.33 (s, 6H, SiMe ₂ ) 1.32 (s, 9H, tert-butyl), 0.99 (d, 6H, iso-propyl-CH ₃ ) ppm. Pseudo-meso: 7.73-6.84 (m, 14H, aromatic H), 6.74 (s, 1H, C = CH), 3.35 (q, 1H, isopropyl CH), 2 , 09, 1.77 (2 × s, 6H, CH ₃ ), 1.53 (s, 3H, SiMe), 1.35, 1.31 (2 × s, 18H, tert-butyl), 1.26 (s, 3H, SiMe), 1.16 (d, 6H, iso-propyl-CH ₃ ) ppm.

polymerization

Mean it
PP = polypropylene
MC = metallocene
Kat = supported catalyst system
h = hour
Ndm ³ = standard liter
Rpm = revolutions per minute
VZ = viscosity number in cm ³ / g
M _w = molar mass weight average in g / mol
M _w / M _n = molar mass distribution, determined by gel permeation chromatography
SD = bulk density in g / dm ³ and
Mp. = Melting point in ° C, determined by differential scanning calorimetry (DSC) at a heating and cooling rate of 10 ° C / min.
TT = triads / tacticity in percent determined by ¹³ C-NMR spectroscopy
RI = regio error in%; determined by ¹³ C-NMR spectroscopy

Example 11 Representation of the supported catalyst system

75.5 mg (0.10 mmol) dimethylsilanediyl- (2,3-dimethyl -4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) - Zirconium dichloride was dissolved at room temperature in 4.3 cm ³ (20 mmol Al) of 30% toluene methylaluminoxane solution (Albemarle Corporation, Baton Rouge, Louisiana, USA). The solution was diluted with 3.7 cm ^{3 of} toluene and stirred at 25 ° C. for 1 h, protected from light. This solution was added in portions to 4.0 g of SiO ₂ (type MS 948, WR Grace, Davison Chemical Devision, Baltimore, Maryland, USA, pore volume 1.6 ml / g, calcined at 600 ° C.) with stirring and the batch was after at the end of the addition, stirred for 10 min. The ratio of the volume of the solution to the total pore volume of the carrier material was 1.25. The mixture was then dried at 40 ° C. and 10 ^-3 mbar within 4 h. 5.5 g of a free-flowing powder were obtained.

polymerization

A dry 16 dm ³ reactor, which had first been flushed with nitrogen and then with propylene, was filled with 10 dm ^{3 of} liquid propylene. 8 cm ^{3 of} 20% triethyl aluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 15 min. A suspension of 2 g of the supported metallocene catalyst in 20 cm ^{3 of} Exxsol was then added to the reactor, heated to the polymerization temperature of 70 ° C. and the polymerization system was kept at 70 ° C. for 1 hour. The polymerization was stopped by degassing and the polymer obtained was dried in vacuo. The result was 2.9 kg of polypropylene powder.
The catalyst activity was 105 kg PP / (g MC × h) or 1.5 kg PP / (g Kat × h)
The isotactic polypropylene shown had the following properties: mp 148 ° C; M _w = 2.6 x 10 ⁵ g / mol, M _w / M _n = 5.0.

Example 12 Representation of the supported catalyst system

78.3 mg (0.10 mmol) of dimethylsilanediyl- (2,3-dimethyl-4- (4'-tert-butylphenyl) -indenyl) - (2-isopropyl-4- (4'-tert-butylphenyl) -indenyl ) -Zirconium dichloride (Example 10) were dissolved at room temperature in 4.3 cm ³ (20 mmol Al) 30% toluene methylaluminoxane solution (Albemarle Corporation, Baton Rouge, Louisiana, USA). The solution was diluted with 3.7 cm ^{3 of} toluene and stirred at 25 ° C. for 1 h, protected from light. This solution was added in portions to 4.0 g of SiO ₂ (type MS 948, WR Grace, Davison Chemical Devision, Baltimore, Maryland, USA, pore volume 1.6 ml / g, calcined at 600 ° C.) with stirring and the batch was after at the end of the addition, stirred for 10 min. The ratio of the volume of the solution to the total pore volume of the carrier material was 1.25. The mixture was then dried at 40 ° C. and 10 ^-3 mbar within 4 h. 5.5 g of a free-flowing powder were obtained.

polymerization

A dry 16 dm ³ reactor, which had first been flushed with nitrogen and then with propylene, was filled with 10 dm ^{3 of} liquid propylene. 8 cm ^{3 of} 20% triethyl aluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 15 min. A suspension of 2 g of the supported metallocene catalyst in 20 cm ^{3 of} Exxsol was then added to the reactor, heated to the polymerization temperature of 70 ° C. and the polymerization system was kept at 70 ° C. for 1 hour. The polymerization was stopped by degassing and the polymer obtained was dried in vacuo. The result was 2.4 kg of polypropylene powder.
The catalyst activity was 77 kg PP / (g MC × h) or 1.2 kg PP / (g Kat × h)
The isotactic polypropylene shown had the following properties: mp 144 ° C; M _w = 3.7 × 10 ⁵ g / mol, M _w / M _n = 7.

Example 13 Representation of the supported catalyst system

78.3 mg (0.10 mmol) dimethylsilanediyl- (2-isopropyl-3-methyl-4- (4'-tert-butylphenyl) -indenyl) - (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride (Example 13) were dissolved at room temperature in 4.3 cm ³ (20 mmol Al) of 30% toluene methylaluminoxane solution (Albemarle Corporation, Baton Rouge, Louisiana, USA). The solution was diluted with 3.7 cm ^{3 of} toluene and stirred at 25 ° C. for 1 h, protected from light. This solution was added in portions to 4.0 g of SiO ₂ (type MS 948, WR Grace, Davison Chemical Devision, Baltimore, Maryland, USA, pore volume 1.6 ml / g, calcined at 600 ° C.) with stirring and the batch was after at the end of the addition, stirred for 10 min. The ratio of the volume of the solution to the total pore volume of the carrier material was 1.25. The mixture was then dried at 40 ° C. and 10 ^-3 mbar within 4 h. 5.5 g of a free-flowing powder were obtained.

polymerization

A dry 16 dm ³ reactor, which had first been flushed with nitrogen and then with propylene, was filled with 10 dm ^{3 of} liquid propylene. 8 cm ^{3 of} 20% triethyl aluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 15 min. A suspension of 2 g of the supported metallocene catalyst in 20 cm ^{3 of} Exxsol was then added to the reactor, heated to the polymerization temperature of 70 ° C. and the polymerization system was kept at 70 ° C. for 1 hour. The polymerization was stopped by degassing and the polymer obtained was dried in vacuo. The result was 3.4 kg of polypropylene powder.
The catalyst activity was 108 kg PP / (g MC × h) or 1.7 kg PP / (g Kat × h). The isotactic polypropylene shown had the following properties: mp 146 ° C.; M _w = 4.0 × 10 ⁵ g / mol, M _w / M _n = 8.

Example 14 Copolymerization with catalyst system Example 11

A dry 5 dm ³ reactor, which had first been flushed with nitrogen and then with propylene, was filled with 3 dm ^{3 of} liquid propylene. 8 cm ^{3 of} 20% triethylaluminum solution in Varsol (Witco) were added as scavengers, 10 bar of ethylene were subsequently injected and the mixture was stirred at 30 ° C. for 15 minutes. A suspension of 1 g of the supported metallocene catalyst in 20 cm ^{3 of} Exxsol was then added to the reactor, heated to the polymerization temperature of 70 ° C. and the polymerization system was kept at 70 ° C. for 1 hour. The polymerization was stopped by degassing and the polymer obtained was dried in vacuo. The result was 2.1 kg of ethylene-propylene copolymer powder.
The catalyst activity was 111 kg PP / PE copolymer / (g MC × h) or 2.1 kg PP-PE / (g Kat × h). The copolymer had the following properties: M _w = 0.57 × 10 ⁵ g / mol, M _w / M _n = 3.6, M _w (copo) / M _w (homo) = 0.48, C2 incorporation : 16.7% by weight.

Comparative example

Analogously to Example 11, a catalyst system with dimethylsilanediylbis- (2-methyl-4- phenylindenyl) zirconium dichloride and it was analogous to Example 14 Copolymerization carried out. The result was 1.9 kg of ethylene-propylene copolymer powder.

The catalyst activity was 130 kg PP / PE copolymer / (g MC × h) or 1.9 kg PP-PE / (g Kat × h). The copolymer had the following properties: M _w = 1.39 × 105 g / mol, M _w / M _n = 2.7, M _w (Copo) / M _w (Homo) = 0.26, C2 incorporation: 6.5% by weight.

Claims (11)

1. Transition metal compound of the formula (I)


wherein


for a two-tier group like


stands and


for a two-tier group like


stands, and in what
M ¹ is titanium, zirconium or hafnium;
R ¹ , R ^{2 are the} same or different and represent a C ₁ -C ₂₀ carbon-containing group;
R ¹ ', R ² ' are the same or different, are the same or different from R ¹ or R ² , and are hydrogen or a C ₁ -C ₂₀ carbon-containing group;
R ^{3 is} a C ₁ -C ₄₀ carbon-containing group or R ³ forms a mono- or polycyclic ring system with R ⁴ , which in turn can optionally be substituted;
R ³ 'is hydrogen or a C ₁ -C ₄₀ carbon-containing group or R ³ ' forms a mono- or polycyclic ring system with R ⁴ ', which in turn can optionally be substituted;
R ⁴ , R ⁴ 'are the same or different and are hydrogen or a C ₁ -C ₂₀ carbon-containing group;
R ⁵ , R ⁵ ', R ⁶ , R ⁶ ' are the same or different and are hydrogen or a C ₁ -C ₂₀ carbon-containing group;
R ^{7 is} a bridging structural element between the two indenyl radicals, selected from the group M ² R ¹⁰ R ¹¹ , in which M ^{2 is} silicon, germanium, tin or carbon and R ¹⁰ and R ^{11 can be the} same or different and hydrogen or a C ₁ -C _{20 represents} hydrocarbon-containing group;
R ⁸ , R ^{9 are} identical or different and are halogen, linear or branched C ₁ -C ₂₀ alkyl, substituted or unsubstituted phenolate, or R ⁸ and R ⁹ are linked to one another and form a mono- or polycyclic ring system, which in turn, if appropriate can be substituted. 2. transition metal compound according to claim 1, characterized in that


For


stands, and


For


stands, wherein the substituents R ³ to R ⁶ and R ³ 'to R ⁶ ' are as defined in formula (I). 3. transition metal compound according to one of claims 1 or 2, characterized in that
M ¹ is zirconium;
R ¹ , R ^{2 are the} same or different and represent a C ₁ -C ₁₂ alkyl group;
R ¹ ', R ² ' are the same or different and are hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, cyclopentyl or cyclohexyl;
R ³ , R ³ 'are the same or different and represent a C ₆ -C ₁₈ aryl group or two radicals R ³ with R ⁴ and / or R ³ ' with R ⁴ 'can form a mono- or polycyclic ring system, which in turn can optionally may be substituted, and R ^{3 may} also be hydrogen;
R ⁴ , R ⁴ 'are the same or different and are either hydrogen or R ⁴ with R ³ and / or R ⁴ ' with R ³ 'form a mono- or polycyclic ring system;
R ⁵ , R ⁵ ', R ⁶ , R ⁶ ' are identical or different and are hydrogen, linear or branched C ₁ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl or C ₃ -C ₁₅ alkylalkenyl; C ₆ -C ₂₀ aryl, C ₄ -C ₁₈ heteroaryl, C ₇ -C ₂₀ arylalkyl; and fluorine-containing C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl, or C ₇ -C ₂₀ arylalkyl;
R ^{7 is} a bridging structural element SiR ¹⁰ R ¹¹ and R ¹⁰ and R ^{11 are} identical or different and are a C ₁ -C ₂₀ hydrocarbon-containing group and
R ⁸ , R ⁹ is chlorine or methyl. 4. ligand system of the formula (II) or its double bond isomers,


where the variables are as defined in formula (I). 5. A process for the preparation of ansa metallocenes of the formula (I), comprising the following steps: a) reacting a 1-indanone of the formula (III) or (III ') with an organometallic compound M ³ R ² _m Hal _n or M ³ R ² ' _m Hal _n and subsequent elimination to the substituted indene of the formula (IV) or (IV '),


where the variables R ¹ , R ¹ ', R ² , R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ', R ⁵ , R ⁵ ', R ⁶ and R ⁶ ' have the meaning as in formula ( I) M ^{3 is} an alkali metal, alkaline earth metal, aluminum or titanium, Hal is halogen, m is an integer and is equal to or greater than 1 and the sum of m + n corresponds to the valence of M ³ ; b) deprotonation of the substituted indene of the formula (IV) or (IV ') and subsequent reaction of the deprotonated indene with compounds of the type R ⁷ X ₂ to give compounds of the formula (V) or (V') or their double bond isomers,


where X is Cl, Br, I or O-tosyl and R ^{7 has} the meaning as in formula I; c) reacting the compound of the formula (V) or (V) with a further deprotonated indene, which was obtained by deprotonating (IV) or (IV '), to the ligand system of the formula (IIa) or its double bond isomers,


d) deprotonation of the ligand system of the formula (IIa) or its double bond isomers and reaction with compounds of the type X ₂ M ¹ R ⁸ R ⁹ to give the ansa- metallocene of the formula (I), where X has the meaning as in formula V and M ¹ , R ⁸ and R ^{9 have} the meanings as in formula (I). 6. Inden of formula (IV) or its double bond isomer,


wherein the variables R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning as in formula I. 7. Catalyst system containing one or more compounds of Formula (I) according to any one of claims 1 to 3 and one or more Cocatalysts and / or carriers. 8. Use of a catalyst system according to claim 7 for Production of a polyolefin, in particular a copolymer from various Olefins. 9. Use of a compound of formula (I) according to one of the Claims 1 to 3 for the production of a polyolefin, in particular a copolymer different olefins. 10. Use according to one of claims 8 or 9 for the production of Ethylene / propylene copolymers. 11. A process for producing a polyolefin by polymerizing a or more olefins in the presence of one or more compounds of formula (I) according to one of claims 1 to 3.