DE10305227A1 - Catalyst system for preparing isotactic polyolefins, is obtainable by reacting chiral transition metal compounds having two bidentate chelating ligands connected to one another via bridge and further monodentate ligand, and cocatalysts - Google Patents

Abstract

A catalyst system is obtainable by reacting chiral transition metal compound(s) and cocatalyst(s) to convert the chiral transition metal compound into a cation. The chiral transition metal compound contains two bidentate chelating ligands connected to one another via a bridge and, if desired, further monodentate ligand(s). A catalyst system for preparing isotactic polyolefins is obtainable by reacting chiral transition metal compound(s) and cocatalyst(s) to convert the chiral transition metal compound into a cation. The chiral transition metal compound contains two bidentate chelating ligands connected to one another via a bridge and, if desired, further monodentate ligand(s). The four coordinating atoms of the two chelating ligands are in an approximately planar arrangement around the transition metal ion and up to two further ligands located above and below this approximately planar coordination sphere formed by the four coordinating atoms of the two chelating ligands and, in the case of two further ligands, these being in the transposition relative to one another. Independent claims are also included for: (a) use of a chiral transition metal compound of structure (Ib) or one of its enantiomers of structure (Ib*) for preparing a catalyst system for the polymerization of olefins; (b) a process for preparing the inventive catalyst system for olefin polymerization, comprising contacting transition metal compound(s) of structures (Ib) or (Ib*) with cation-forming compound(s); (c) a process for preparing isotactic polyolefins by polymerization of alpha -olefin(s) in the presence of the inventive catalyst system; (d) a polyolefin obtained by the above process; (e) a polyolefin composition comprising the above polyolefin; and (f) a film, fiber, or molding produced from the polyolefin composition. [Image] M : zirconium or hafnium.

Description

The present invention relates to Catalyst systems for the production of isotactic polyolefins obtainable from Implementation of at least one chiral transition metal compound and at least one cocatalyst capable of the chiral transition metal compound to convert into a cation, whereby the chiral transition metal compound two over a bridge interconnected bidentate Chelating ligands and optionally one or two further monodentate ligands contains the four coordinating atoms of the two chelate ligands being the transition metal ion nearly planar and up to two more ligands are located above and below this by the four coordinating atoms of the two Chelating ligands formed approximately Planar coordination sphere and for the case of two such further ligands these are in transposition to one another stand.

In addition, the present concerns Invention the use of the catalyst systems according to the invention for Production of polyolefins, a process for the production of Polyolefins by polymerization or copolymerization at least an olefin in the presence of one of the catalyst systems according to the invention, the use of chiral transition metal compounds for the production of a catalyst system for the polymerization of Olefins, chiral transition metal compounds, a process for the preparation of a catalyst system for olefin polymerization, a process for the production of isotactic polyolefins, polyolefins available according to a method according to the invention, Polyolefin compositions containing the polyolefins according to the invention and products made from such polyolefin compositions.

Research and development for Use of organic transition metal compounds, in particular of metallocenes as catalyst components for the polymerization and copolymerization of olefins with the aim of producing customized Polyolefins have been intense at universities over the past 15 years and operated in industry.

In addition to the metallocenes increasingly new classes of transition metal compounds investigated as catalyst components that do not contain cyclopentadienyl ligands contain.

Macromolecules 1997, 30, 171-175 Ethylene bis (salicylideniminato) zirconium dichloride and its use shown as a catalyst component in the polymerization of ethylene. The polymerization of higher α-olefins how propylene has not been studied.

In Adv. Synth. Catal. 2002, 344, No. 5, transition metal complexes of metals of group 4 of the Periodic Table of the Elements Phenoxyiminliganden described. The transition metal ion is in these complexes octahedrally surrounded by two phenoxyimine ligands and two chloride ions, with the two oxygen atoms in the trans position and the two Nitrogen atoms and the two chlorine atoms in the cis position to each other stand. Dependent on on the cocatalyst and the substitution pattern of the phenoxyimine ligands describe polypropylenes with different tacticities. While a highly syndiotactic polypropylene is described with the presented catalyst systems in addition to atactic polypropylene an isotactic polypropylene with a low melting point and low isotacticity been obtained.

In Chem. Commun., 2002, 352-353 transition metal complexes each with a biaryl-bridged one Bisphenoxyimine ligands and two chlorine ligands, their use in of ethylene polymerization and opportunities described the catalyst deactivation. The presented transition metal complexes of titanium and zircon show a structure in which the metal ion is surrounded octahedron and the two oxygen atoms in the trans position and the two nitrogen atoms and the two chlorine atoms in the cis position to stand by each other.

In WO 99/56699 various chiral bis (salicylidene) -1,2-diaminocyclohexane transition metal complexes listed, some of which are also commercially available. There will be none Olefin polymerizations described.

Object of the present invention was to find catalyst systems based on non-metallocenes, that allow highly isotactic polyolefins, especially isotactic polypropylenes with melting points above 150 ° C. Furthermore, should the catalyst systems are characterized by good activities and in technical relevant polymerization temperatures can be used.

Accordingly, the above-mentioned catalyst systems found.

The chiral transition metal compound contains a metal cation an element of the 3rd, 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic table of the elements or an element of the lanthanides, for example scandium, Yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, Molybdenum, Tungsten, manganese, iron, cobalt, nickel or palladium are preferred Titanium, zirconium, hafnium and chromium, particularly preferably zirconium, Hafnium and chrome.

The bridge of the chiral transition metal compound is preferably a chiral bridge, in particular a bridge which contains two chiral sp ³ -hybridized carbon atoms which are each directly connected to one of the two chelate ligands. A bridge in which the two chiral sp ³ -hybridized carbon atoms are directly connected to one another is particularly preferred.

Each of the two bidentate chelating ligands is preferably simply negatively charged. The two coordinating Atoms of the chelating ligand are, for example, nitrogen, phosphorus, Oxygen, sulfur, selenium or tellurium, especially nitrogen, Oxygen or sulfur. At least one is preferred, in particular accurate one of the two coordinating atoms of the bidentate chelate ligand is a nitrogen atom. A bidentate chelate ligand with a coordinating nitrogen atom and a coordinating oxygen atom.

Also preferred is a bidentate chelate ligand, that with the metal ion a five-membered or six-membered, especially a six-membered metallacycle formed.

Also preferred are bidentate chelate ligands, each about one of the two coordinating atoms, in particular each via one Nitrogen atom bridged together are. extraordinarily bidentate are preferred Chelate ligands with an imine function derived from 1,3-dicarbonyl compounds, such as acetylacetone, benzoylacetone or 1,3-diphenyl-1,3-propanedione and substituted derivatives thereof, or derived from ortho-carbonylphenol derivatives, such as 2-hydroxybenzaldehyde or 2-hydroxyacetophenone and substituted Derivatives thereof, the imine function by reaction of a Carbonyl function with a primary Amine is formed.

The monodentate ligands are simply negatively charged anions, in particular halide anions such as fluoride, chloride, bromide or iodide anions, in particular chloride anions, hydride anions, C ₁ -C ₄₀ hydrocarbon anions such as methyl, tert-butyl -, Vinyl, phenyl or benzyl anions, alkoxy or aryloxy anions such as methoxy or phenoxy anions, and amide anions such as dimethylamide anions. Particularly preferred monodentate ligands are chloride, methyl and benzyl anions, especially chloride anions.

The four coordinating atoms of the two bidentate Chelate ligands surround the transition metal ion nearly planar. The transition metal ion does not have to exactly in that of the four coordinating atoms of the two bidentate chelate ligands formed level. In the sense of the present invention means nearly planar that the four coordinating atoms of the two chelating ligands do not have to lie exactly on one level, but the two coordinating ones Atoms of the first chelating ligand versus the two coordinating ones Atoms of the second chelating ligand can be slightly twisted. in the The present case is under an approximately planar environment of the Metal ions through the four coordinating atoms of the two chelating ligands understood that the angle that a first level made up of the two coordinating atoms of the first chelate ligand and the transition metal ion is formed with a second level consisting of the two coordinating Atoms of the second chelate ligand and the transition metal ion are formed will include in the range from 0 ° to 20 °, in particular in the range from 0 ° to 10 °.

worin
M ein Element der 3., 4., 5., 6., 7., 8., 9. oder 10. Gruppe des Periodensystems der Elemente oder der Lanthaniden ist,
Z gleich oder verschieden sein kann und ein organischer oder anorganischer anionischer Ligand ist,
n1, n2 gleich oder verschieden sein können und 0 oder 1 sind, wobei n1 + n2 + 2 der Wertigkeit von M entspricht,
R¹ und R² gleich oder verschieden sein können und ein C₁-C₄₀-kohlenstoffhaltiger Rest sind, oder
R¹ und R² zusammen mit den sie verbindenden Atomen ein cyclisches oder polycyclisches Ringsystem bilden, das im Ringsystem anstelle von Kohlenstoffatomen ein oder mehrere, gleiche oder verschiedene Heteroatome, ausgewählt aus der Gruppe bestehend aus den Elementen N, O, P, S und Si enthalten kann,
R³ Wasserstoff oder ein C₁-C₄₀-kohlenstoffhaltiger Rest ist, wobei R³ eine geringere sterische Hinderung aufweist als R¹,
R⁴ Wasserstoff oder ein C₁-C₄₀-kohlenstoffhaltiger Rest ist, wobei R⁴ eine geringere sterische Hinderung aufweist als R²,
R⁵ und R⁶ gleich oder verschieden sein können und Wasserstoff oder ein C₁-C₄₀-kohlenstoffhaltiger Rest sind, oder
R¹ und R³, R² und R⁴, R¹ und R⁵ und/oder R² und R⁶ zusammen mit den sie verbindenden Atomen jeweils ein cyclisches oder polycyclisches Ringsystem bilden, das im Ringsystem anstelle von Kohlenstoffatomen ein oder mehrere, gleiche oder verschiedene Heteroatome, ausgewählt aus der Gruppe bestehend aus den Elementen N, 0, P, S und Si enthalten kann,
X für eine Einfachbindung zwischen den beiden Kohlenstoffatomen oder für eine zweibindige Gruppe steht,
Y¹, Y² gleich oder verschieden sein können und für Sauerstoff, Schwefel, Selen, Tellur, eine NR⁹-Gruppe oder eine PR⁹-Gruppe stehen,
R⁷, R⁸, R⁹ gleich oder verschieden sein können und für Wasserstoff, C₁-C₂₀-Alkyl, C₂-C₂₀-Alkenyl, C₆-C₂₂-Aryl, Alkylaryl oder Arylalkyl mit 1 bis 10 Kohlenstoffatomen im Alkylrest und 6 bis 22 Kohlenstoffatomen im Arylrest stehen,
T¹ T², T³ und T⁴ gleich oder verschieden sein können und Wasserstoff oder ein C₁-C₄₀-kohlenstoffhaltiger Rest sind, oder T¹ und T³ und/oder T² und T⁴ zusammen mit den sie verbindenden Kohlenstoffatomen jeweils ein cyclisches oder polycyclisches Ringsystem bilden, das im Ringsystem anstelle von Kohlenstoffatomen ein oder mehrere, gleiche oder verschiedene Heteroatome, ausgewählt aus der Gruppe bestehend aus den Elementen N, O, P, S und Si enthalten kann.Catalyst systems as described above are preferred, characterized in that the chiral transition metal compound is characterized by a transition metal compound of the formula (1) or its enantiomer of the formula (I *)

wherein
M is an element of the 3rd, 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic Table of the Elements or the lanthanides,
Z can be the same or different and is an organic or inorganic anionic ligand,
n1, n2 can be the same or different and are 0 or 1, where n1 + n2 + 2 corresponds to the valence of M,
R ¹ and R ^{2 may be the} same or different and are a C ₁ -C ₄₀ carbon-containing radical, or
R ¹ and R ² together with the atoms connecting them form a cyclic or polycyclic ring system which, in the ring system instead of carbon atoms, has one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si can contain
R ^{3 is} hydrogen or a C ₁ -C ₄₀ carbon-containing radical, where R ³ has less steric hindrance points as R ¹ ,
R ^{4 is} hydrogen or a C ₁ -C ₄₀ carbon-containing radical, R ⁴ having a lower steric hindrance than R ² ,
R ⁵ and R ^{6 may be the} same or different and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical, or
R ¹ and R ³ , R ² and R ⁴ , R ¹ and R ⁵ and / or R ² and R ⁶ together with the atoms connecting them each form a cyclic or polycyclic ring system which one or more of the same in the ring system instead of carbon atoms or can contain various heteroatoms selected from the group consisting of the elements N, 0, P, S and Si,
X represents a single bond between the two carbon atoms or a double bond group,
Y ¹ , Y ^{2 may be the} same or different and represent oxygen, sulfur, selenium, tellurium, an NR ⁹ group or a PR ⁹ group,
R ⁷ , R ⁸ , R ^{9 may be the} same or different and represent hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₂ aryl, alkylaryl or arylalkyl having 1 to 10 carbon atoms in the Alkyl radical and 6 to 22 carbon atoms in the aryl radical,
T ¹ T ² , T ³ and T ^{4 can be the} same or different and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical, or T ¹ and T ³ and / or T ² and T ⁴ together with the carbon atoms connecting them in each case form a cyclic or polycyclic ring system which can contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si in the ring system instead of carbon atoms.

M ¹ is an element of the 3rd, 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic Table of the Elements or the lanthanides, for example scandium, yttrium, titanium, zirconium, hafnium, vanadium , Niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel or palladium, preferably titanium, zirconium, hafnium or chromium, particularly preferably zirconium, hafnium and chromium, and extremely preferably zirconium.

The radical Z can be the same or different, preferably the same, and is an organic or inorganic anionic ligand. Z is preferably halogen, such as fluorine, chlorine, bromine or iodine, in particular chlorine, hydrogen, C ₁ -C ₂₀ -, preferably C _{1 -4} -alkyl, C ₂ -C ₂₀ -, preferably C ₂ -C ₄ -alkenyl , C ₆ -C ₂₂ -, preferably C ₆ -C ₁₀ aryl, alkylaryl or arylalkyl having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10 carbon atoms in the aryl radical, -OR ⁷ or - NR ⁷ R ⁸ . Z is particularly preferably chlorine or methyl.

n1, n2 can be the same or different be and are 0 or 1, where n1 + n2 + 2 corresponds to the valence of M. N1 and n2 are preferred for the elements of the 4th group of the periodic table of the elements are the same and 1, which results in an oxidation number of +4 and for the elements the 10th group of the periodic table of the elements equal and 0, from which an oxidation number of +2 results.

R ¹ and R ² may be the same or different, preferably equal to, and are a C ₁ -C ₄₀ -radical, such as a C ₁ -C ₄₀ -hydrocarbon radical or C ₃ -C _{4 0} -Si (R ⁷⁾ _3, or R ¹ and R ² together with the atoms connecting them form a cyclic or polycyclic ring system which, in the ring system instead of carbon atoms, has one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si , preferably N, O or S, in particular N may contain. R ¹ and R ² are preferably a cyclic, branched or unbranched C ₁ -C ₂₀ -, preferably C ₁ -C ₈ -alkyl radical, a C ₂ -C _{2 0} -, preferably C ₂ -C ₈ -alkenyl radical, a C ₆ -C ₂₂ -, preferably C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10 carbon atoms in the aryl radical, the Residues can also be halogenated, or C ₃ -C ₁₈ -, preferably C ₃ -C ₈ -Si (R ⁷ ) ₃ or R ¹ and R ² together with the atoms connecting them form a cyclic 4 to 8, preferably 5 or capable of carrying in turn, C ₁ -C _{2 0} carbonaceous residues 6-membered ring system. R ¹ and R ² are particularly preferably a cyclic, branched or unbranched C ₁ -C 8 -alkyl radical, a C ₆ -C ₁₀ -aryl radical, an alkylaryl or arylalkyl radical with 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms Atoms in the aryl radical or trimethylsilyl or R ¹ and R ² together with the atoms connecting them form a cyclic 5 or 6-membered ring system, which in turn is cyclic, branched or unbranched C ₁ -C ₈ alkyl radicals, a C ₆ -C ₁₀ aryl radical , Alkylaryl or arylalkyl radicals having 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical or trimethylsilyl radicals. Examples of particularly preferred radicals R ¹ and R ² are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n -Heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl , 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl , Phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl. Examples of particularly preferred ring systems formed from the radicals R ¹ , R ² and the atoms connecting them are 1,2-cyclohexylene, 1,2-cyclopentylene or 1-benzylpyrrolidin-3,4-ylene.

R ³ is hydrogen or a C ₁ -C ₄₀ carbon-containing radical such as, for example, a C ₁ -C ₄₀ coal water or C ₃ -C _{4 0} -Si (R ⁷ ) ₃ , where R ^{3 has} a lower steric hindrance than R ¹ . R ³ is preferably hydrogen, a cyclic, branched or unbranched, in particular unbranched C ₁ -C ₂₀ -, preferably C ₁ -C ₈ -alkyl radical, a C ₂ -C _{2 0} -, preferably C ₂ -C ₈ -alkenyl radical C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl, an alkylaryl or arylalkyl radical, preferably arylalkyl radical having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10, carbon atoms in the aryl radical, where the radicals can also be halogenated. R ³ is particularly preferably hydrogen or an unbranched C ₁ -C ₈ -alkyl radical. R ³ is extremely preferably hydrogen.

R ⁴ is hydrogen or a C ₁ -C ₄₀ carbon-containing radical such as a C ₁ -C ₄₀ hydrocarbon radical or C ₃ -C ₄₀ -Si (R ⁷ ) ₃ , where R ^{4 has} a lower steric hindrance than R ² . R ⁴ is preferably hydrogen, a cyclic, branched or unbranched, in particular unbranched C ₁ -C ₂₀ -, preferably C ₁ -C ₈ -alkyl radical, a C ₂ -C ₂₀ -, preferably C ₂ -C ₈ -alkenyl radical, a C. ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical, preferably arylalkyl radical having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10, carbon atoms in the Aryl radical, where the radicals can also be halogenated. R ⁴ is particularly preferably hydrogen or an unbranched C ₁ -C ₈ -alkyl radical. R ⁴ is extremely preferably hydrogen.

The steric hindrance of a residue is determined by the fact that it is filled with space. For example, steric hindrance increases in the following series:
Hydrogen <methyl <ethyl <isopropyl <tert-butyl
R ⁵ and R ⁶ can be the same or different, in particular the same, and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical. R ⁵ and R ⁶ are preferably hydrogen, a cyclic, branched or unbranched C ₁ -C ₂₀ -, preferably C ₁ -C ₈ alkyl, a C ₂ -C ₂₀ , preferably C ₂ -C ₈ alkenyl, a C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl, an alkylaryl or arylalkyl radical with 1 to 10 , preferably 1 to 4 carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10 carbon atoms in the aryl radical, where the radicals can also be halogenated. R ⁵ and R ⁶ are particularly preferably hydrogen, a cyclic, branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₆ -C ₁₀ -aryl radical, an alkylaryl or arylalkyl radical with 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical. Examples of particularly preferred radicals R ⁵ and R ⁶ are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl , n-heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, pentafluorophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2 , 6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di- (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl , 2-naphthyl, phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl, especially hydrogen.

Furthermore, two radicals R ¹ and R ³ , R ² and R ⁴ , R ¹ and R ⁵ and / or R ² and R ⁶ together with the atoms connecting them can form a cyclic or polycyclic ring system, which in the ring system instead of carbon atoms may contain one or more, identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, in particular N, O and S.

X stands for a single bond between the two carbon atoms or for a double bond group. Examples of double-bonded groups X are CR ⁷ R ⁸ , in particular CH ₂ , CR ⁷ R ⁸ -CR ⁷ R ⁸ , in particular CH ₂ -CH ₂ , (CR ⁷ R ⁸ ) ₃ , (CR ⁷ R ⁸ ) ₄ or (CR ⁷ R ⁸ ) ₅ . X is preferably a single bond or CH ₂ , in particular a single bond.

Y ¹ and Y ² can be the same or different, in particular the same, and represent oxygen, sulfur, selenium, tellurium, an NR ⁹ group or a PR ⁹ group, in particular oxygen.

R ⁷ , R ⁸ and R ⁹ can be the same or different and stand for hydrogen, C ₁ -C ₂₀ -, preferably C ₁ -C ₄ -alkyl, C ₂ -C ₂₀ -, preferably C ₂ -C ₄ -alkenyl, C ₆ -C ₂₂ -, preferably C ₆ -C ₁₀ aryl, alkylaryl or arylalkyl having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10 carbon atoms in the aryl radical.

T ¹ , T ² , T ³ and T ⁴ can be the same or different and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical, or T ¹ and T ³ and / or T ² and T ⁴ form together with those connecting them Carbon atoms are each a cyclic or polycyclic ring system which can contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si in the ring system instead of carbon atoms. T ¹ , T ² , T ³ and T ^{4 are} preferably a cyclic, branched or unbranched C ₁ -C ₂₀ -, preferably C ₁ -C ₈ -alkyl radical, a C ₂ -C _{2 0} -, preferably C ₂ -C _8- alkenyl radical, a C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10, C. -Atoms in the aryl radical, where the radicals can also be halogenated, or T ¹ and T ³ and / or T ² and T ⁴ together with the carbon atoms connecting them each form substituted or unsubstituted, aromatic or partially hydrogenated 5- to 8-membered, in particular Form 5- or 6-membered ring systems which can contain heteroatoms selected from the group consisting of O, S and N and which in turn can be part of larger polycyclic ring systems. T ¹ and T ³ and T ² and T ⁴ together with the two connecting carbon atoms particularly preferably form substituted or unsubstituted phenyl rings, thiophene rings or pyrrole rings, ins special phenyl rings, which in turn can be part of larger polycyclic ring systems.

The radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , T ¹ , T ² , T ³ and T ⁴ can also contain functional groups according to the invention, without the polymerization properties to change the catalyst system according to the invention as long as these functional groups are chemically inert under the polymerization conditions.

Unless further restricted, the substituents according to the present invention are further defined as follows:
The term "C ₁ -C ₄₀ carbon-containing radical", as used herein, denotes C ₁ -C ₄₀ alkyl radicals, C ₁ -C ₁₀ fluoroalkyl radicals, C ₁ -C ₁₂ alkoxy radicals, saturated C ₃ -C ₂₀ heterocyclic radicals Residues, C ₆ -C ₄₀ aryl residues, C ₂ -C ₄₀ heteroaromatic residues, C ₆ -C ₁₀ fluoroaryl residues, C ₆ -C ₁₀ aryloxy residues, C ₃ -C ₁₈ trialkylsilyl residues, C ₂ -C ₂₀ alkenyl residues , C ₂ -C ₂₀ alkynyl radicals, C ₇ -C ₄₀ arylalkyl radicals or C ₈ -C ₄₀ arylalkenyl radicals.

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. Preferred is 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 Cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, sec-butyl or tert-butyl.

The term "alkenyl" as used herein includes linear or single or, if appropriate, multiple branched hydrocarbons with at least one, possibly also several C-C double bonds, which accumulate or can be alternated.

The term “saturated heterocyclic radical”, as used in the present context, denotes mono- or polycyclic, substituted or unsubstituted hydrocarbon radicals in which one or more carbon atoms, CH groups and / or CH ₂ groups are selected by hetero atoms from the group consisting of O, S, N and P. Preferred examples of substituted or unsubstituted saturated heterocyclic radicals are pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl and the like, and with methyl-, isopropyl, propyl, and tert-butyl residues substituted derivatives thereof.

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 ₁₈ alkoxy, C ₂ -C ₁₀ alkenyl or C. mono- ₃ -C _{1 5} -Alkylalkenyl or may be substituted multiple times. Preferred examples of substituted and unsubstituted aryl radicals are, in particular, phenyl, pentafluorophenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthryl, 9-phenanthryl , 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl or 4-trifluoromethylphenyl.

The term "heteroaromatic radical" as used herein denotes 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 furyl, thienyl, pyrrolyl, pyridyl, 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 "alkylalkenyl" as used herein includes linear or single or, if appropriate, multiple branched hydrocarbons with at least one, possibly also several C-C double bonds, which are isolated, so the substituent has both alkyl and alkenyl segments having.

The term "arylalkyl" as used herein denotes aryl-containing substituents whose aryl radical is linked via an alkyl chain to the corresponding rest of the molecule connected is. Preferred examples are benzyl, substituted benzyl, phenethyl, substituted phenethyl and the like.

With fluoroalkyl and fluoroaryl means that at least one, preferably several and at most all hydrogen atoms of the corresponding substituent are replaced by fluorine atoms. Examples preferred according to the invention fluorine-containing substituents are trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorophenyl, 4-trifluoromethylphenyl, 4-perfluoro-tert-butylphenyl and the like.

worin
M ein Element der 4. oder 6. Gruppe des Periodensystems der Elemente ist,
Z gleich oder verschieden sein kann und Halogen, Wasserstoff, C₁-C₁₀-Alkyl, C₆-C₁₄-Aryl, Alkylaryl oder Arylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylrest und 6 bis 10 Kohlenstoffatomen im Arylrest ist,
n1, n2 gleich oder verschieden sein können und 0 oder 1 sind, wobei n1 + n2 + 2 der Wertigkeit von M entspricht,
R¹ und R² gleich oder verschieden sein können und ein C₁-C₄₀-kohlenstoffhaltiger Rest sind, oder R¹ und R² zusammen mit den sie verbindenden Atomen ein cyclisches oder polycyclisches Ringsystem bilden, das im Ringsystem anstelle von Kohlenstoffatomen ein oder mehrere, gleiche oder verschiedene Heteroatome, ausgewählt aus der Gruppe bestehend aus den Elementen N, O, P, S und Si enthalten kann,
R⁵ und R⁶ gleich sind und Wasserstoff oder einen C₁-C₄₀-kohlenstoffhaltigen Rest bedeuten,
R¹⁰, R¹¹, R^{1 2} und R^{1 3} gleich oder verschieden sein können und Wasserstoff oder einen C₁-C₄₀-kohlenstoffhaltigen Rest bedeuten, oder zwei benachbarte Reste R¹⁰, R¹¹, R^{1 2} und R^{1 3} zusammen mit den sie verbindenden beiden Kohlenstoffatomen ein cyclisches Ringsystem bilden können.Catalyst systems as described above are particularly preferred, characterized in that the chiral transition metal compound of the formula (I) or (I *) is characterized by a transition metal compound of the formula (Ia) or its enantiomer of the formula (Ia *),

wherein
M is an element of the 4th or 6th group of the Periodic Table of the Elements,
Z can be the same or different and is halogen, hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₄ aryl, alkylaryl or arylalkyl having 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical,
n1, n2 can be the same or different and are 0 or 1, where n1 + n2 + 2 corresponds to the valence of M,
R ¹ and R ^{2 may be the} same or different and are a C ₁ -C ₄₀ carbon-containing radical, or R ¹ and R ² together with the atoms connecting them form a cyclic or polycyclic ring system which, instead of carbon atoms, has one or more in the ring system may contain identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si,
R ⁵ and R ^{6 are} identical and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical,
R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3 may be the} same or different and denote hydrogen or a C ₁ -C ₄₀ carbon-containing radical, or two adjacent radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} together can form a cyclic ring system with the two carbon atoms connecting them.

M ¹ is an element of the 4th or 6th group of the Periodic Table of the Elements, for example titanium, zirconium, hafnium, chromium, molybdenum or tungsten, preferably titanium, zirconium, hafnium or chromium, particularly preferably zirconium and hafnium, and extremely preferably zirconium.

The radical Z can be identical or different, preferably the same, and is halogen, such as fluorine, chlorine, bromine or iodine, in particular chlorine, hydrogen, C ₁ -C ₁₀ -, preferably C ₁ -C ₄ -alkyl, C ₆ -C _{1 4} -, preferably C ₆ -C ₁₀ aryl and alkylaryl or arylalkyl having 1 to 4 carbon atoms in the alkyl radical and 6 to 10, preferably 6 carbon atoms in the aryl radical. Z is preferably chlorine, benzyl or methyl, in particular chlorine.

The radicals R ¹ and R ² can be the same or different, in particular the same, and are a C ₁ -C ₄₀ carbon-containing radical such as, for example, a C ₁ -C ₄₀ hydrocarbon radical or C ₃ -C ₄₀ -Si (R ⁷ ) ₃ , or R ¹ and R ² together with the atoms connecting them form a cyclic or polycyclic, in particular a monocyclic ring system which, in the ring system instead of carbon atoms, has one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P. , S and Si, preferably N, O or S, in particular N may contain. R ¹ and R ² are preferably a cyclic, branched or unbranched C ₁ -C _{2 0} , preferably C ₁ -C ₈ alkyl radical, a C ₂ -C _{2 0} , preferably C ₂ -C ₈ alkenyl radical, a C. ₆ -C ₂₂ -, preferably C ₆ -C ₁₀ aryl, an alkylaryl or arylalkyl radical having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10, carbon atoms in the aryl radical, where the radicals may also be halogenated, or C ₃ -C _{1 8} -, C ₃ -C _8, preferably -Si (R ⁷⁾ ₃ or R ¹ and R ² together with the atoms connecting them form a cyclic 4 to 8, preferably 5 or 6-membered ring system, which in turn can carry C ₁ -C ₂₀ carbon-containing radicals. R ¹ and R ² are particularly preferably a cyclic, branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₆ -C ₁₀ -aryl radical, an alkylaryl or arylalkyl radical with 1 to 4 C atoms in the alkyl radical and 6 to 10 C. -Atoms in the aryl radical or trimethylsilyl or R ¹ and R ² together with the atoms connecting them form a cyclic 5 or 6-membered ring system, which in turn is cyclic, branched or unbranched C ₁ -C ₈ -alkyl radicals, a C ₆ -C ₁₀ - Aryl radicals, alkylaryl or arylalkyl radicals having 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical or trimethylsilyl radicals can carry. Examples of particularly preferred radicals R ¹ and R ² are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n -Heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl , 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl . Phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl. Examples of particularly preferred ring systems formed from the radicals R ¹ , R ² and the atoms connecting them are 1,2-cyclohexylene, 1,2-cyclopentylene or 1-benzylpyrrolidin-3,4-ylene.

The radicals R ⁵ and R ⁶ are identical and denote hydrogen or a C ₁ -C ₄₀ carbon-containing radical. R ⁵ and R ⁶ are preferably hydrogen, a cyclic, branched or unbranched C ₁ -C ₂₀ -, preferably C ₁ -C _8- alkyl radical, a C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10, C. -Atoms in the aryl radical, where the radicals can also be halogenated. R ⁵ and R ⁶ are particularly preferably hydrogen, a cyclic, branched or unbranched C ₁ -C ₈ -alkyl radical, a C ₆ -C ₁₀ -aryl radical, an alkylaryl or arylalkyl radical with 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical. Examples of particularly preferred radicals R ⁵ and R ⁶ are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl , n-heptyl, n-octyl, benzyl, 2-phenylethyl, phenyl, pentafluorophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2 , 6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di- (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl , 2-naphthyl, phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p-trimethylsilylphenyl, especially methyl, phenyl or hydrogen, especially hydrogen.

The R ⁷ radicals can be the same or different and represent C _1-4 alkyl such as methyl, ethyl or tert-butyl, in particular methyl, C ₆ -C ₁₀ aryl such as phenyl or naphthyl, in particular phenyl, alkylaryl or arylalkyl with 1 to 4 carbon atoms in the alkyl radical and 6 to 10, preferably 6 carbon atoms in the aryl radical.

The radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} can be the same or different and mean hydrogen or a C ₁ -C ₄₀ carbon-containing radical such as a C ₁ -C ₄₀ hydrocarbon radical or C ₃ -C ₄₀ -Si (R ⁷ ) ₃ , or two adjacent radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} , together with the two carbon atoms connecting them, can form a cyclic ring system which, if appropriate, instead of carbon atoms, has one or more identical or different heteroatoms, selected from the group consisting of the elements N, O, P, S and Si, preferably N, O or S. The radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3 are} preferably hydrogen, a cyclic, branched or unbranched C ₁ -C ₂₀ , preferably C ₁ -C ₈ alkyl radical, a C ₆ -C ₂₂ , preferably C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl radical and 6 to 22, preferably 6 to 10, carbon atoms in the aryl radical, where the radicals can also be halogenated, or C ₃ -C _{1 8} -, preferably C ₃ -C ₈ -Si (R ⁷ ) ₃ or two adjacent radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} together with the two carbon atoms connecting them form a cyclic 4 bis 8-, preferably 5 or 6-, in particular 6-membered ring system, which in turn can carry C ₁ -C ₂₀ carbon-containing radicals. The radicals R ¹⁰ , R ¹¹ , R ¹² and R ^{1 3} are particularly preferably hydrogen, a cyclic, branched or unbranched C ₁ -C ₈ alkyl radical, a C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical with 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical or trimethylsilyl or two adjacent radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} together with the two carbon atoms connecting them form a cyclic 5 or 6-membered ring system , which in turn carry cyclic, branched or unbranched C ₁ -C ₈ alkyl radicals, a C ₆ -C ₁₀ aryl radical, alkylaryl or arylalkyl radicals having 1 to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical or trimethylsilyl radicals can. Examples of particularly preferred radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ¹³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, adamantyl, benzyl, triphenylmethyl, 1,1-diphenylethyl, 1-methyl-1-phenylethyl, 2-phenylethyl, phenyl, pentafluorohenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di- (tert-butyl ) -phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-isopropylphenyl, p-tert-butylphenyl, ps-butylphenyl, p-cyclohexylphenyl and p- trimethylsililphenyl. Examples of particularly preferred ring systems formed from two adjacent radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ¹³ together with the two carbon atoms connecting them are a phenyl ring, pyridine ring or thiophene ring.

R ¹⁰ , R ¹¹ , R ^{1 2} and R ¹³ with the same indices are preferably the same radical.

The radical R ¹⁰ is preferably not equal to hydrogen and represents a bulky radical, such as a branched or cyclic C ₁ -C ₁₀ alkyl radical, a C ₆ -C ₁₀ aryl radical, an alkylaryl or arylalkyl radical with 1 to 4 carbon atoms in the Alkyl radical and 6 to 10 carbon atoms in the aryl radical. Examples of particularly preferred radicals R ¹⁰ isopropyl, t-butyl, cyclohexyl, adamantyl, triphenylmethyl, 1,1-diphenylethyl, 1-methyl-1-phenylethyl, phenyl, pentafluorophenyl, 3 , 5-di- (tert-butyl) phenyl, 2,4,6-trimethylphenyl, 1-naphthyl, phenanthryl, p-tert-butylphenyl. An example of a particularly preferred ring system formed from the radicals R ¹⁰ and R ¹¹ together with the two carbon atoms connecting them is a phenyl ring.

Illustrative but non-limiting examples of transition metal compounds which can be used as a component of the catalyst systems according to the invention are:

The preparation of the bridged chelating ligands and the chiral transition metal compounds produced therefrom is known in principle from the literature and for example in WO 99/56699 described.

The cocatalyst, which together with the closer above described chiral transition metal compound the polymerization-active according to the invention Catalyst system is able to form the chiral transition metal compound to convert into a cation.

Suitable cation-forming compounds are, for example, compounds of the aluminoxane type strong neutral Lewis acid, an ionic compound with a Lewis acid cation or an ionic compound with Bronsted acid as a cation. An aluminoxane is preferred as a cocatalyst.

R^{1 4} eine C₁-C₄-Alkylgruppe bedeutet, bevorzugt eine Methyl- oder Ethylgruppe und m für eine ganze Zahl von 5 bis 30, bevorzugt 10 bis 25 steht.The compounds described in WO 00/31090, for example, can be used as aluminoxanes. Open-chain or cyclic aluminoxane compounds of the general formulas (II) or (III) are particularly suitable.

R ^{1 4 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.

The preparation of these oligomeric Aluminoxane compounds are usually made by implementing a solution of trialkyl aluminum with water. As a rule, they are included obtained oligomeric aluminoxane compounds as mixtures different long, both linear and cyclic chain molecules, so that m is to be regarded as the mean. The aluminoxane compounds can also in a mixture with other metal alkyls, preferably with aluminum alkyls available.

Furthermore, instead of the aluminoxane compounds of the general formulas (II) or (III) also modified aluminoxanes are used, some of which contain hydrocarbon residues or hydrogen atoms through alkoxy, aryloxy, siloxy or amide radicals are replaced.

It has proven to be beneficial the chiral transition metal compound and to use the aluminoxane compounds in such amounts that the atomic relationship between aluminum from the aluminoxane compounds and the transition metal from the transition metal compound in the range from 10: 1 to 1000: 1, preferably in the range from 20: 1 to 500: 1 and in particular in the range from 30: 1 to 400: 1.

Compounds of the general formula (IV) are strong, neutral Lewis acids M ² X ¹ X ² X ³ (IV) preferred in which
M ^{2 is} 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 are independently hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C _{1 5} aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine, in particular for haloaryl, preferably for pentafluorophenyl.

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

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

Strong neutral Lewis acids that the reaction products are also suitable as cation-forming compounds from the reaction of a boronic acid with two equivalents of an aluminum trialkyl or the reaction products from the reaction an aluminum trialkyl with two equivalents of an acidic fluorinated one, in particular perfluorinated carbon compound such as pentafluorophenol or bis (pentafluorophenyl) boric acid.

Salt-like compounds of the cation of the general formula (V) are ionic compounds with Lewis acid cations. [(Y ^{a +} ) Q ₁ Q ₂ ... Q _z ] ^{d +} (V)
suitable in which
Y is an element of the 1st to 16th group of the Periodic Table of the Elements, Q ₁ to Q _z are singly negatively charged groups such as C ₁ -C ₂₈ -alkyl, C ₆ -C _{1 5} aryl, alkylaryl, arylalkyl, haloalkyl, Halogenaryl each having 6 to 20 carbon atoms in the aryl and 1 to 28 carbon atoms in the alkyl radical, C ₃ -C ₁₀ cycloalkyl, which can optionally be substituted by C ₁ -C ₁₀ alkyl groups, halogen, C ₁ -C , C ₆ -C _{1 5} aryloxy, silyl or mercaptyl groups are ₂₈ alkoxy,
a for integers from 1 to 6 and
z represents integers from 0 to 5, and
d corresponds to the difference a – z, but d is greater than or equal to 1.

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

Salts with non-coordinating anions can also by combining a boron or aluminum compound, e.g. an aluminum alkyl, with a second compound obtained by reaction can link two or more boron or aluminum atoms, e.g. Water and a third compound, that with the boron or aluminum compound forms an ionizing ionic compound, e.g. triphenylchloromethane, getting produced. additionally can be a fourth compound, also with the boron or aluminum compound responds, e.g. Pentafluorophenol, can be added.

Ionic compounds with Bronsted acids as Cations preferably also have non-coordinating counterions. As Brönsted acid in particular protonated amine or aniline derivatives are preferred. preferred Cations are N, N-dimethylanilinium, N, N-dimethylcylohexylammonium and N, N-dimethylbenzylammonium and derivatives of the latter two.

Preferred ionic compounds the cation-forming compounds are, in particular, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylcyclohexylammonium 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 the surface of a carrier particle.

Other suitable cation-forming Compounds are listed in WO 00/31090.

The amount of strong, neutral Lewis acids, ionic Compounds with Lewis Acidic Cations or Ionic Compounds with Brönsted acids as Cations are usually 0.1 to 20 equivalents, preferably 1 to 10 equivalents, based on the chiral transition metal compound.

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

You can also mix all of them beforehand mentioned cation-forming compounds are used. 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.

Preferably both the transition metal compound as well as the cation-forming compounds in a solvent used, with aromatic hydrocarbons having 6 to 20 carbon atoms, especially xylenes and toluene are preferred.

The catalyst system according to the invention can additionally contain a metal compound of the general formula (VI), M ³ (R ¹⁵ ) _r (R ¹⁶ ) _s (R ¹⁷ ) _t (VI) in which M ³ denotes an alkali metal, an alkaline earth metal or a metal from the 13th group of the Periodic Table of the Elements, ie boron, aluminum, gallium, indium or thallium,
R ^{15 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 ¹⁶ and R ^{17 are the} same or different and 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 mean
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 ³ ,
contain, wherein the metal compound of formula (VI) is usually not identical to the cation-forming compound. Mixtures of different metal compounds of the formula (VI) can also be used.

Of the metal compounds of the general formula (VI), those are preferred in which
M ^{3 is} lithium, magnesium or aluminum and R ¹⁶ and R ^{17 are} C ₁ -C ₁₀ alkyl.

Particularly preferred metal compounds of the formula (VI) are n-butyllithium, n-butyl-n-octyl-magnesium, n-butyl-n-heptyl-magnesium, Tri-n-hexyl aluminum, tri-iso-butyl aluminum, triethyl aluminum and trimethyl aluminum and mixtures thereof.

If a metal compound of the formula (VI) is used, it is preferably present in the catalyst system according to the invention in an amount such that the molar ratio of M ³ from formula (VI) to transition metal from the chiral transition metal compound is from 800: 1 to 1: 1, in particular from 200: 1 to 2: 1.

The catalyst system according to the invention particularly preferably contains additionally a carrier.

Such a supported catalyst system to get the strapless Catalyst system with a support be implemented. In principle, the order of assembly is from carrier, the chiral transition metal compound and the cocatalyst as desired. The chiral transition metal compound and the cocatalyst can independently fixed from each other or simultaneously. After the individual The solid can be processed using suitable inert solvents such as B. aliphatic or aromatic hydrocarbons become.

Fine carriers are preferably used as carriers carrier used any organic or inorganic, inert Can be solid. In particular, the carrier a porous Solid such as talc, a layered silicate, an inorganic oxide or a finely divided 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 example, 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 be subjected to a thermal treatment, for example 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 ) ₂ 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 fine particles Polyolefin powder (e.g. polyethylene, polypropylene or polystyrene) can are also used and should preferably also be used before Use of adhering moisture, solvent residues or others Contamination from appropriate cleaning and drying operations be freed. It can also functional polymer carriers, z. B. on the basis of polystyrenes, are used on the 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 according to the invention at least one chiral transition metal compound in a suitable solvent with at least one cocatalyst as a cation-forming compound brought into contact, preferably a soluble reaction product Adduct or a mixture is obtained.

The preparation thus obtained is then with the dehydrated or inerted carrier material mixed, the solvent removed and the resulting supported transition metal compound catalyst system dried to ensure that the solvent is complete or mostly from the pores of the carrier material Will get removed. The worn one Catalyst is considered to be free flowing Get powder. examples for the technical implementation of the above method is described in WO 96/00243, WO 98/40419 or WO 00/05277.

Another preferred embodiment is, initially to generate the cation-forming compound on the carrier component and subsequently this supported cation-forming compound with the chiral transition metal compound in To get in touch.

• 1. Komponente: mindestens eine definierte Bor- oder Aluminiumverbindung,
• 2. Komponente: mindestens eine neutrale Verbindung, die mindestens ein acides Wasserstoffatom besitzt,
• 3. Komponente mindestens ein Träger, bevorzugt ein anorganischer oxidischer Träger und optional als 4. Komponente eine Base, bevorzugt eine organische stickstoffhaltige Base, wie zum Beispiel ein Amin, ein Anilinderivat oder ein Stickstoffheterocyclus.

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

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

worin
R¹⁸ gleich oder verschieden sind und Wasserstoff, Halogen, C₁-C₂₀-Alkyl, C₁-C₂₀-Halogenalkyl, C₁-C₁₀-Alkoxy, C₆-C₂₀-Aryl, C₆-C₂₀-Halogenaryl, C₆-C₂₀-Aryloxy, C₇-C₄₀-Arylalky, C₇-C₄₀-Halogenarylalkyl, C₇-C₄₀-Alkylaryl, C7-C₄₀-Halogenalkylaryl bedeuten, oder R¹⁸ ist eine OSiR^{1 9} ₃-Gruppe, worin
R^{1 9} gleich oder verschieden sind und Wasserstoff, Halogen, C₁-C₂₀-Alkyl, C₁-C₂₀-Halogenalkyl, C₁-C₁₀-Alkoxy, C₆-C₂₀-Aryl, C₆-C₂₀-Halogenaryl, C6-C₂₀-Aryloxy, C₇-C₄₀-Arylalkyl, C₇-C₄₀-Halogenarylalkyl, C₇-C₄₀-Alkylaryl, C₇-C₄₀-Halogenalkylaryl, bevorzugt Wasserstoff, C₁-C₈-Alkyl oder C₇-C₂₀-Arylalkyl bedeuten, und
M⁴ gleich Bor oder Aluminium, bevorzugt Aluminium ist.The boron or aluminum compound used in the preparation of these supported cocatalysts are preferably those of the formula (VII)

wherein
R ^{18 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 arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C7-C ₄₀ haloalkylaryl, or R ¹⁸ is an OSiR ^{1 9} ₃ Group where
R ^{1 9 are} identical 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, C6-C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, 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 ⁴ is boron or aluminum, preferably aluminum.

Particularly preferred as compounds of the formula (VII) are trimethyl aluminum, triethyl aluminum and To name tri-isobutyl aluminum.

worin
R²⁰ gleich oder verschieden Wasserstoff, Halogen, eine borfreie C₁-C₄₀-kohlenstoffhaltige Gruppe wie C₁-C₂₀-Alkyl, C₁-C₂₀-Halogenalkyl, C₁-C₁₀-Alkoxy, C₆-C₂₀-Aryl, C₆-C₂₀-Halogenaryl, C₆-C₂₀-Aryloxy, C₇-C₄₀-Arylalky, C₇-C₄₀-Halogenarylalky, C₇-C₄₀-Alkylaryl, C₇-C₄₀-Halogenalkylaryl, eine Si(R²²)₃-Gruppe oder eine CH(SiR²² ₃)₂-Gruppe bedeutet, worin
R²² eine borfreie C₁-C₄₀-kohlenstoffhaltige Gruppe wie C₁-C₂₀-Alkyl, C₁-C₂₀-Halogenalkyl, C₁-C₁₀-Alkoxy, C₆-C₂₀-Aryl, C₆-C₂₀-Halogenaryl, C₆-C₂₀-Aryloxy, C₇-C₄₀-Arylalky, C₇-C₄₀-Halogenarylalky, C₇-C₄₀-Alkylaryl, C7-C₄₀-Halogenalkylaryl ist, und
R²¹ eine zweibindige C₁-C₄₀-kohlenstoffhaltige Gruppe wie C₁-C₂₀-Alkylen, C₁-C₂₀-Halogenalkylen, C₆-C₂₀-Arylen, C₆-C₂₀-Halogenarylen, C₇-C₄₀-Arylalkylen, C₇-C₄₀-Halogenarylalkylen, C₇-C₄₀-Alkylarylen, C₇-C₄₀-Halogenalkylarylen bedeutet,
D ein Element der 16. Gruppe des Periodensystems der Elemente oder eine NR²³-Gruppe ist, worin R²³ Wasserstoff oder ein C₁-C₂₀-Kohlenwasserstoffrest wie C₁-C₂₀-Alkyl oder C₆-C₂₀-Aryl ist, bevorzugt Sauerstoff und
h 1 oder 2 ist.The neutral compounds which have at least one acidic hydrogen atom and can react with compounds of the formula (VII) are preferably compounds of the formulas (VIII), (IX) or (X),

wherein
R ^20, 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 ²² ) ₃ group or a CH (SiR ²² ₃ ) ₂ group, wherein
R ^{22 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 arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C7-C ₄₀ haloalkylaryl, and
R ^{21 is} a divalent C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkylene, C ₁ -C ₂₀ haloalkylene, C ₆ -C ₂₀ arylene, C ₆ -C ₂₀ haloarylene, C ₇ -C ₄₀ Arylalkylene, C ₇ -C ₄₀ -haloarylalkylene, C ₇ -C ₄₀ -alkylarylene, C ₇ -C ₄₀ -haloalkylarylene,
D is an element of the 16th group of the Periodic Table of the Elements or an NR ²³ group, in which R ^{23 is} hydrogen or a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₂₀ alkyl or C ₆ -C ₂₀ aryl, prefers oxygen and
h is 1 or 2.

Suitable compounds of the formula (VIII) are water, alcohols, phenol derivatives, thiophenol derivatives or Aniline derivatives, especially the halogenated ones and in particular the perfluorinated alcohols and phenols are important. Examples for special 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 (IX) are boronic acids and boric acids, boric acids with perfluorinated aryl radicals, such as (C ₆ F ₅ ) ₂ BOH, being particularly noteworthy.

Suitable compounds of the formula (X) 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 connections of formula (VII) with compounds of formula (VIII) or (X) Trimethyl aluminum / pentafluorophenol, trimethyl aluminum / 1-bis (pentafluorophenyl) methanol, trimethyl aluminum / 4-hydroxy-2,2 ', 3,3', 4,4 ', 5,5', 6,6'-nonafluorobiphenyl, triethyl aluminum / Pentafluorophenol or Triisobutylaluminum / pentafluorophenol or triethylaluminum / 4,4'-dihydroxy-2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl hydrate, for example Implementation products of the following type can be formed.

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

The principle is the combination any of the components.

If necessary, the implementation products from the reaction of at least one compound of the formula (VII) with at least one compound of formula (VIII), (IX) or (X) and optionally the organic nitrogen base with an organometallic compound of formula (II), (III), (IV) and / or (VI) combined, then with the carrier the supported cocatalyst system to build.

In a preferred embodiment the 1st component, e.g. B. Compounds of formula (VII), and the 2nd component, e.g. B. Compounds of formulas (VIII), (IX) or (X), as well as a carrier Combine separately as 3rd component and a base as 4th component and subsequently implemented with one another, the reaction preferably in an inert Solvents or suspending agents takes place. The supported cocatalyst formed can of inert solvents and suspending agents be freed before it with the chiral transition metal compound and optionally a metal compound of the formula (VI) for the catalyst system according to the invention is implemented.

It is also possible to prepolymerize the catalyst solid according to the invention 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.

Furthermore, as an additive during or after the preparation of the supported catalyst system according to the invention 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 be added. The molar ratio of additives to chiral transition metal compounds is usually from 1: 1000 to 1000: 1, preferably from 1: 5 to 20: 1.

The catalyst systems according to the invention Base of the above closer described chiral transition metal compounds are characterized by the fact that they are compared to the previously known Catalyst systems isotactic polyolefins, especially isotactic Polypropylene, with a higher melting point deliver.

Further objects of the invention are a the use of a catalyst system according to the invention such described above for the production of polyolefins and the other process for the production of polyolefins by polymerization or copolymerization at least one olefin in the presence of a catalyst system according to the invention as described above.

As a rule, the catalyst system according to the invention is used together with a further metal compound of the general formula (VI), which differs from that in the preparation of the invention according to the catalyst system used metal compounds of formula (VI) can be used for the polymerization or copolymerization of olefins. The further metal compound is generally added to the monomer or the suspending agent and is used to purify the monomer from substances which can impair the catalyst activity. It is also possible to add one or more further cation-forming compounds to the catalyst system according to the invention in the polymerization process.

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 act, including acrylic-substituted α-olefins.

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, or R ^m and R ⁿ together with the atoms connecting them can form one or more rings.

Examples of such olefins are 1-olefins with 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 methylnorbornene. Ethylene, propylene, 1-butene, 1-hexene or 4-methyl-1-pentene are preferred.

Propylene or ethylene, in particular propylene, are particularly preferably homopolymerized using the catalyst system according to the invention, or ethylene is combined with 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, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene copolymers, ethylene / propylene / ethylidene norbornene or ethylene / propylene / 1,4-hexadiene terpolymers.

The polymerization can be done in a known manner Way in bulk, in suspension, in the gas phase or in a supercritical Medium in the usual, for the Polymerization of olefins used 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 Gas phase process or gas phase fluidized bed process into consideration. As a solvent or suspending agents inert hydrocarbons, for example isobutane, or else Monomers themselves can be used.

The polymerization can take place at temperatures in the range of -60 up to 300 ° C and press in the range of 0.5 to 3000 bar. Are preferred Temperatures in the range from 50 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 mean dwell 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 activity in the polymerization Hydrogen can be used. Common additives such as antistatic agents can also be used can also be used. The catalyst system according to the invention can be used for polymerization can be used directly, which means that it is pure into the polymerization system introduced, or it becomes better dosing with inert components like paraffins, oils or growing.

They are particularly suitable catalyst systems according to the invention for the production of propylene homopolymers with high melting points.

worin die Variablen die Bedeutung wie in den Formeln (I) und (I*) haben.The invention furthermore relates to the use of a chiral transition metal compound of the formula (Ib) or its enantiomer of the formula (Ib *) for the preparation of a catalyst system for the polymerization of olefins,

where the variables have the meaning as in formulas (I) and (I *).

worin die Variablen die Bedeutung wie in den Formeln (Ia) und (Ia*) haben.The use of the chiral transition metal compounds of the formula (Ic) or (Ic *) is particularly preferred for the preparation of a catalyst system.

where the variables have the meaning as in the formulas (Ia) and (Ia *).

Another object of the invention are chiral transition metal compounds of the formulas (Ib) or (Ib *), characterized in that M is the same Zirconium or hafnium; especially zirconium.

Further objects of the invention are Process for the preparation of a catalyst system for olefin polymerization containing the reaction of at least one transition metal compound Formulas (Ib) or (Ib *) with at least one cation-forming compound and a process for producing isotactic polyolefins by polymerizing at least one α-olefin in the presence of a catalyst system produced according to the process just mentioned

Another object of the invention are those according to one of the above-mentioned polymerization processes available Polyolefins, especially homopolymers and copolymers of propylene as well as polyolefin compositions which with the catalyst systems of the invention available Contain polyolefins.

The isotactic polypropylenes which can be prepared by the process according to the invention are distinguished by a viscosity number (IV) greater than 1, a melting temperature (T _m ) greater than 158 ° C., preferably greater than 160 ° C., in particular greater than 163 ° C. Isotaktizitätsrate determined by Pentadenanalyse from the ¹³ C-NMR of the polymer samples of greater than 98%, in particular greater than 99% of a regio-error rate determined by Pentadenanalyse from the ^{1 3} C-NMR of the polymer samples of less than 0.3%, in particular of less than 0 , 25% and a polydispersity Q = Mw / Mn less than 3, in particular less than 2.5.

The according to the inventive method produced polymers and polyolefin compositions containing them are particularly suitable for the production of films, fibers and moldings.

Another object of the invention are also foils, fibers or moldings made from the foregoing described polyofefin compositions.

The invention is characterized by the following however, the invention is not restricted to examples.

Examples

General information

The synthesis and handling of organometallic Compounds and the catalysts were carried out with the exclusion of Air and moisture under argon protective gas (glove box and Schlenk technology). All solvents used were flushed with argon before use and absoluteized via molecular sieve.

(S, S) - (+) N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane, (R, R) - (-) N, N'-bis - (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane and (S, S) - (+) N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane chromium (III) chloride were commercially available.

In the production of supported catalyst systems a silica of the type XPO 2107 from Grace was used as the silica gel, that at 180 ° C in vacuum for Was dried for 18 hours.

Determination of the melting temperature:

The melting temperature T _m was determined by DSC measurement according to ISO standard 3146 in a first heating phase with a heating rate of 20 ° C per minute to 200 ° C, a dynamic crystallization with a cooling rate of 20 ° C per minute to 25 ° C and one second heating phase again with a heating rate of 20 ° C per minute to 200 ° C. The melting temperature was then the temperature at which the enthalpy versus temperature curve measured in the second heating phase showed the maximum.

Gel Permeation Chromatography:

Gel permeation chromatography (GPC) was carried out at 145 ° C. in 1,2,4-trichlorobenzene, using a 150C GPC apparatus from Waters. The data was evaluated using the Win-GPC software from HS-Entwicklungsgesellschaft for scientific hard and software mbH, Ober-Hilbersheim. The columns were calibrated using polypropylene standards with molecular weights of 100 to 10 ⁷ g / mol. Mass averages (M _w ) and number averages (M _n ) of the molecular weights of the polymers were determined. The Q value is the ratio of the mass average (M _w ) to the number average (M _n ).

Determination of the viscosity number (I.V.):

The viscosity number was determined in an Ubbelohde viscometer PVS 1 with a measuring head S 5 (both from Lauda) in decalin at 135 ° C. To prepare the sample, 20 mg of polymer were dissolved in 20 ml of decalin at 135 ° C. for 2 h. 15 ml of the solution were added to the viscometer, the device led min. three runtime measurements until a consistent result was achieved. The IV was calculated from the running times using IV = (t / t ₀ - 1) · 1 / c with t: mean value of the running time of the solution, t ₀ :: mean value of the running time of the solvent, c: concentration of the solution in g / ml ,

Example 1: Synthesis of (S, S) - (+) - N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-titanium (IV) dichloride (1)

A solution of 1g (1.8 mmol) (S, S) - (+) N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane in 70 ml of diethyl ether was added 1.4 ml of a solution of n-butyllithium in hexane (3.6 mmol, 2.5M) was slowly added to the room temperature. The yellow solution was stirred at room temperature for 1.5 hours and then treated with 0.34 g (1.8 mmol) of TiCl ₄ . The reaction mixture was stirred at room temperature for 18 h, then filtered and the solvent removed in an oil pump vacuum. There were 0.85 g. (1) obtained as a red, free flowing powder.

Example 2: Synthesis of (S, S) - (+) - N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-zirconium (IV) dichloride (2)

A solution of 2.94 g (5.38 mmol) (S, S) - (+) N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane in 100 ml 6.8 ml of a solution of n-butyllithium in hexane (10.9 mmol, 1.6M in hexane) was slowly added to diethyl ether at room temperature and the reaction mixture was stirred for 4 h. Subsequently, 1.24 g (5.34 mmol) of ZrCl _{4 were} added in portions and the reaction mixture was stirred overnight. The solvents were then removed in an oil pump vacuum, the solid was taken up in dichloromethane, filtered and dichloromethane was removed from the filtrate in an oil pump vacuum. 4.06 g (2) were obtained as a bright yellow, free-flowing powder.

Example 3: Synthesis of (R, R) - (-) - N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-zirconium (IV) dichloride (3)

Analogously to Example 2, a solution of 3.3 g (6.04 mmol) (R, R) - (-) - N, N'-bis- (3,5-di-tert-butylsalicylidene) -1, 2-diaminocyclohexane in 100 ml of diethyl ether with 7.55 ml of a solution of n-butyllithium in hexane (12.08 mmol, 1.6 M). 1.4 g (6.04 mmol) of ZrCl _{4 were then} added. After working up analogously to Example 2, 4.77 g (3) were obtained as a bright yellow, free-flowing powder. Crystals were obtained from a saturated solution of (3) in methylene chloride

X-ray crystal structure analysis: The 1a and 1b show the structure of the connection (3) from different perspectives.

Example 4 Homopolymerization from propene

In a 1 liter reactor, 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M). At 30 ° C Poured 250 g of propylene and the reactor contents heated to a temperature of 50 ° C. A catalyst solution made by adding 10 mg of the titanium compound (1) (15.1 μmol) Example 1 and 2.5 ml of a solution of methylalumoxane in toluene (3.95 mmol, 10% by weight) and then 15 minutes After-reaction, was together with 50 g of 80 ° C hot propylene in the reactor introduced. The reactor contents were stirred at 50 ° C for 0.5 hours and the polymerization reaction is terminated by relaxing the reactor. 5 ml of methanol were added to the reactor contents. The polymer was Vacuum over Dried overnight. 2.00 g of polypropylene were obtained. The results the polymerization and the results of the polymer analysis are in the following table 1 compiled.

Example 5 Homopolymerization from propene

The polymerization became analogous to Example 4 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) were combined with 250 g propylene at 30 ° C submitted and at 50 ° C. heated. A Catalyst solution prepared by adding 10 mg of the zirconium compound (2) (14.1 µmol) Example 2 and 2.5 ml of a solution of methylalumoxane in toluene (3.95 mmol, 10% by weight) and then 15 minutes After-reaction, was together with 50 g of 80 ° C hot propylene in the reactor introduced. The reactor contents were stirred at 50 ° C for 0.5 hours. To Completion of the reaction and workup of the polymer were 3.30 g of polypropylene obtained. The results of the polymerization and the Results of the polymer analysis are in the table below 1 compiled.

2 shows the ^{1 3} C-NMR spectrum of the polymer. The evaluation of the ^{1 3} C-NMR gave a value of 99.2% for the mmmm pentads. Regio errors could not be detected.

Example 6 Homopolymerization from propene (corresponds to 00022-176)

The polymerization became analogous to Example 4 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) and 5 ml MAO (7.9 mmol, 10% by weight) were placed together with 250 g of propylene at 30 ° C. 50 ml of hydrogen are added and the mixture is warmed to 50.degree. A catalyst solution made by adding 20 mg of the zirconium compound (2) (28.3 μmol) Example 2 and 3.9 ml of a solution of Methylalumoxane in toluene (6.2 mmol, 10% by weight) and then 15 minutes After-reaction, was together with 50 g of 80 ° C warm propylene in the reactor introduced. The reactor was heated to 70 ° C and the contents of the reactor for 0.5 Hours at 70 ° C touched. After the reaction was completed and the polymer worked up Received 18 g of polypropylene. The results of polymerization and the results of the polymer analysis are in the table below 1 compiled.

Example 7 Homopolymerization from propene

The polymerization became analogous to Example 6 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) and 5 ml MAO (7.9 mmol, 10% by weight) were placed together with 250 g of propylene at 30 ° C. 50 ml of hydrogen are added and the mixture is warmed to 50.degree. A catalyst solution made by adding 10 mg of the zirconium compound (2) (14.1 μmol) Example 2 and 3.9 ml of a solution of Methylalumoxane in toluene (6.2 mmol, 10% by weight) and then 15 minutes After-reaction, was together with 50 g of 80 ° C hot propylene in the reactor introduced. The reactor contents were stirred at 70 ° C for 0.5 hours. To The reaction was terminated and the polymer worked up g of polypropylene obtained. The results of the polymerization and the Results of the polymer analysis are in the table below 1 compiled.

Example 8 Homopolymerization from propene

The polymerization became analogous to Example 4 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) were combined with 250 g propylene at 30 ° C submitted and at 50 ° C. heated. A Catalyst solution prepared by adding 10 mg (S, S) - (+) N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane chromium (III) chloride (15.8 μmol) and 3.3 ml of a solution of methylalumoxane in toluene (15.8 mmol, 30% by weight) and then 15 minutes After-reaction, was together with 50 g of 80 ° C hot propylene in the reactor introduced. The reactor contents were stirred at 70 ° C for 1.0 hours. To Completion of the reaction and workup of the polymer became 0.15 g of polypropylene obtained. The results of the polymerization and the Results of the polymer analysis are shown in Table 1 below compiled.

Example 9 Copolymerization of propene with ethylene

The polymerization became analogous to Example 8 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) were combined with 250 g propylene at 30 ° C submitted and at 50 ° C. heated. A Catalyst solution prepared by adding 10 mg (S, S) - (+) N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane chromium (III) chloride (15.8 μmol) and 3.3 ml of a solution of methylalumoxane in toluene (15.8 mmol, 30% by weight) and then 15 minutes After-reaction, was fed into the reactor together with 50 g of propylene at 80 ° C. The reactor contents were at 70 ° C heated, ethylene was pressurized to 2 bar in the reactor was given and it was for 1.0 hours at 70 ° C touched. After the reaction was completed and the polymer worked up 1.9 g of polymer obtained. The results of the polymerization are in the following table 1 compiled.

Example 10 Homopolymerization from propene

The polymerization became analogous to Example 8 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) were combined with 250 g propylene at 30 ° C submitted, 100 ml of hydrogen added and heated to 50 ° C. A Catalyst solution prepared by combining 5 mg (S, S) - (+) N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane chromium (III) chloride (15.8 μmol) and 3.3 ml of a solution of methylalumoxane in toluene (15.8 mmol, 30% by weight) and then 15 minutes After-reaction, was together with 50 g of 80 ° C hot propylene in the reactor introduced. The reactor contents were stirred at 70 ° C for 0.5 hours. To Completion of the reaction and workup of the polymer became 4.8 g of polypropylene obtained. The results of the polymerization are in the following table 1 compiled.

Table 1

Example 11 Carrying (S, S) - (+) - N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-zirconium (IV) dichloride

1 g of silica gel was dissolved in 15 ml of toluene suspended, 70.3 mg (S, S) - (+) - N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-zirconium (IV) dichloride (2) (0.1 mmol) added and boiled under reflux for 2 hours. It came into being yellow powder, the protruding one solution was colorless. Toluene was removed and the powder for 2 hours in an oil pump vacuum dried. 1.1 g of yellow powder were obtained.

Example 12 Homopolymerization from propene

The polymerization was carried out analogously to Example 4. 4 ml of a solution of triisobutylaluminum in hexane (4 mmol, 1 M) were placed together with 250 g of propylene at 30 ° C. and the reactor contents were heated to 50 ° C. 50 ml of hydrogen were added at 50.degree. Then 8.4 ml of a 30% solution of methylalumoxane in toluene (40 mmol) were first injected and then 0.402 g of the powder prepared in Example 11 was suspended in 2 ml of hexane together with 50 g of 80 ° C. warm propylene in the reactor introduced. The reactor was heated to 70 ° C and the reactor contents were stirred at 70 ° C for 0.5 hours. After the reaction had ended and the polymer had been worked up, 8.4 g of polypropylene, which had a melting point of 162.1 ° C., were obtained.

Example 13 Carrying (S, S) - (+) - N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-zirconium (IV) dichloride

2 g of silica gel were at room temperature suspended in 10 ml of toluene and 5.2 ml of 30% MAO solution in Toluene was slowly added dropwise. The mixture was stirred for 2 hours and filtered and the backlog 1 hour in an oil pump vacuum dried. 56.7 mg (0.08 mmol) (S, S) - (+) - N, N'-bis- (3,5-di-tert-butylsalicylidene) -1,2-diaminocyclohexane-zirconium (IV) dichloride (2) were dissolved in 8 ml of toluene, with 0.9 ml of 30% MAO solution in Toluene added and stirred for 1 hour. The dried, MAO-treated silica gel was suspended in 10 ml of toluene and the zircon complex MAO solution slowly added to it. After stirring for 1 hour, toluene was removed and the solid in an oil pump vacuum dried. 3.19 g of a yellow, free-flowing powder were obtained receive.

Example 14 Homopolymerization from propene

The polymerization became analogous to Example 4 performed. 4 ml of a solution of triisobutyl aluminum in hexane (4 mmol, 1 M) were combined with 250 g propylene at 30 ° C submitted and the reactor contents heated to 50 ° C. 50 ml of hydrogen were added at 50.degree. Then 2.288 g of the powder prepared in Example 13 were suspended in hexane together with 50 g 80 ° C warm propylene introduced into the reactor. The reactor was to 70 ° C heated, and the reactor content for 0.5 hours at 70 ° C touched. After the reaction was completed and the polymer worked up 4.3 g of polypropylene were obtained, which had a melting point of 151.1 ° C.

Claims (14)

Catalyst system for the production of isotactic Polyolefins available by reacting at least one chiral transition metal compound and at least one cocatalyst capable of the chiral transition metal compound to convert into a cation, whereby the chiral transition metal compound two over a bridge interconnected bidentate Chelating ligands and optionally one or two further monodentate ligands contains the four coordinating atoms of the two chelate ligands being the transition metal ion nearly planar and up to two more ligands are located above and below this by the four coordinating atoms of the two Chelating ligands formed approximately planar coordination sphere and for the case of two such further ligands these are in transposition to one another stand. Catalyst system according to claim 1, wherein the chiral transition metal compound is characterized by a transition metal compound of the formula (I) or its enantiomer of the formula (I *),

wherein M is an element of the 3rd, 4th, 5th, 6th, 7th, 8th, 9th or 10th group of the Periodic Table of the Elements or the lanthanides, Z can be the same or different and an organic or inorganic anionic Is ligand, n1, n2 can be identical or different and are 0 or 1, where n1 + n2 + 2 corresponds to the valence of M, R ¹ and R ^{2 may be the} same or different and are a C ₁ -C ₄₀ carbon-containing radical, or R ¹ and R ² together with the atoms connecting them form a cyclic or polycyclic ring system which, instead of carbon atoms, has one or more in the ring system may contain identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, R ^{3 is} hydrogen or a C ₁ -C ₄₀ carbon-containing radical, where R ^{3 has} a lower steric hindrance than R ¹ , R ^{4 is} hydrogen or a C ₁ -C ₄₀ carbon-containing radical, where R ^{4 has} a lower steric hindrance than R ² , R ⁵ and R ^{6 can be the} same or different and is hydrogen or a C ₁ -C ₄₀ - are carbon-containing radical, or R ¹ and R ³ , R ² and R ⁴ , R ¹ and R ⁵ and / or R ² and R ⁶ together with the atoms connecting them each form a cyclic or polycyclic ring system which in the ring system instead of carbon atoms may contain one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, X represents a single bond between the two carbon atoms or a double bond group, Y ¹ , Y ^{2 are the} same or can be different and represent oxygen, sulfur, selenium, tellurium, an NR ⁹ group or a PR ⁹ group, R ⁷ , R ⁸ , R ^{9 can be the} same or different and represent hydrogen, C ₁ -C ₂₀ - Alkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₂ aryl, alkylaryl or arylalkyl having 1 to 10 carbon atoms in the alkyl radical and 6 to 22 carbon atoms in the aryl radical, T ¹ T ² , T ³ and T ^{4 are} identical or different can be and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical, or T ¹ and T ³ and / or T ² and T ⁴ together with the carbon atoms connecting them each form a cyclic or polycyclic ring system which in the ring system instead of carbon atoms one or more, same or r can contain various heteroatoms selected from the group consisting of the elements N, O, P, S and Si. Catalyst system according to claim 2, characterized in that the chiral transition metal compound of the formula (I) or (I *) is characterized by a transition metal compound of the formula (Ia) or its enantiomer of the formula (Ia *),

wherein M is an element of the 4th or 6th group of the Periodic Table of the Elements, Z may be the same or different and are halogen, hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C _{1 4} aryl, alkylaryl or arylalkyl having from 1 is up to 4 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical, n1, n2 can be identical or different and are 0 or 1, where n1 + n2 + 2 corresponds to the valence of M, R ¹ and R ^{2 can be} identical or different and are a C ₁ -C ₄₀ carbon-containing radical, or R ¹ and R ² together with the atoms connecting them form a cyclic or polycyclic ring system which, in the ring system instead of carbon atoms, has one or more identical or different heteroatoms selected from the group consisting of the elements N, O, P, S and Si, R ⁵ and R ^{6 are the} same and are hydrogen or a C ₁ -C ₄₀ carbon-containing radical, R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} may be the same or different and hydrogen or a C ₁ -C ₄₀ carbon hal term radical, or two adjacent radicals R ¹⁰ , R ¹¹ , R ^{1 2} and R ^{1 3} together with the two carbon atoms connecting them can form a cyclic ring system. Catalyst system according to one of claims 1 to 3 characterized in that the cocatalyst is an aluminoxane is. Catalyst system according to one of claims 1 to 4 which additional a carrier contains. Use of a catalyst system according to one of claims 1 to 5 for the production of polyolefins. Process for the preparation of polyolefins by Polymerization or copolymerization of at least one olefin in Presence of a catalyst system according to one of claims 1 to 5th Use of a chiral transition metal compound of the formula (Ib) or its enantiomer of the formula (Ib *)

wherein the variables have the meanings given in claim 2 for the preparation of a catalyst system for the polymerization of olefins. Chiral transition metal compound of the formulas (Ib) or (Ib *) according to claim 8, in which M is zirconium or hafnium. Process for the preparation of a catalyst system for olefin polymerization comprising the reaction of at least one transition metal compound of the formulas (Ib) or (Ib *) according to claim 8 with at least one cation-forming compound. Process for the production of isotactic polyolefins by polymerizing at least one α-olefin in the presence of a Catalyst system produced by a method according to claim 10th Polyolefins available according to a method according to claim 7 or claim 11. Polyolefin composition containing a polyolefin according to claim 12th Films, fibers or moldings made from polyofine compositions according to claim 13th