EP1771484A1

EP1771484A1 - Method for producing ultrahigh molecular weight polymers while using unbridged metallocene catalysts

Info

Publication number: EP1771484A1
Application number: EP05773455A
Authority: EP
Inventors: Jens Ehlers; Jens Panitzky; Tim Dickner; Jörg SCHOTTEK
Original assignee: Ticona GmbH
Current assignee: Ticona GmbH
Priority date: 2004-07-21
Filing date: 2005-07-19
Publication date: 2007-04-11
Also published as: DE102004035308A1; WO2006008127A1

Abstract

The invention relates to a method for producing ultrahigh molecular weight polymers by polymerizing and copolymerizing olefins while using catalysts and catalyst systems thereof.

Description

Ticona GmbH

Process for the preparation of ultra-high molecular weight polymers using unbridged metallocene catalysts.

The present invention relates to a process for the production of ultra-high molecular weight polymers by polymerization and copolymerization of olefins using catalysts and their catalyst systems. Furthermore, the invention relates to novel catalysts for the polymerization of olefins to ultrahigh molecular weight products.

Ultrahigh molecular weight polymers of ethylene are said to have a viscometrically determined molecular weight of greater than 1 × 10 ⁶ mol / g. Such polymers are widely used because of their exceptional properties such as high abrasion resistance and low sliding friction. That is how you find it

Use in conveyor technology, in bulk handling and also in medical technology as joint pans in artificial joints.

Because of these special properties, the processing of ultra-high molecular weight polyethylene is very expensive. Methods used for the

Production of molded parts are the ram extrusion and pressure-pressing of powdery starting materials, wherein the moldings produced often still have characteristics of the starting powder. Films and fibers are obtained by so-called solution or gel processes, which require a large amount of solvents. One goal is therefore new ultra-high molecular weight

To develop polyethylenes, which are characterized by improved processability.

According to the current state of the art, ultra high molecular weight polyethylenes are prepared by the low pressure process with heterogeneous so-called Ziegler

Catalysts produced. Such catalysts are described, for example, in the following patents: EP186995, DE3833445, EP575840 and US20020045537. Other known catalysts for olefin polymerization are so-called "single-site catalysts." According to the current state of the art, ultrahigh molecular weight polymers can only be produced with them in exceptional cases and under economically unviable conditions.For example, so-called "constrained-geometry" catalysts form ultrahigh molecular weight polyethylenes heterogeneous phase with only moderate activities and morphologies.With so-called phenoxy-imine catalysts, UHMWPEs are obtained only with low activities in economically unviable temperature ranges, examples of which and also for other metallocenes are disclosed in WO9719959, WO0155231, Adv. Synth. Catal., 2002, 344 , 477-493, EP0798306 and also in EP0643078.

Surprisingly, single-site catalysts having a suitable ligand structure have now been found which not only allow the production of ultra-high molecular weight polyethylenes but also provide products having improved processability.

The present invention is a process for the preparation of ultra-high molecular weight polymers using compounds of the formula I.

wherein: M ^{1 represents} a transition metal of the 3rd to 6th group of the Periodic Table of the Elements, the oxidation state of which is not equal to zero, and preferably Ti, Zr, Hf, V,

Mo, Sc, Y, Cr and Nb are, and

R ¹ , R ² , R ³ , R ⁴ , R ^{5 are} each the same or different and are hydrogen or a halogen atom or a Ci - C ₂ o- carbon-containing group, of which two or more can form a cyclic system with each other, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^{10 are} each the same or different and are hydrogen or a halogen atom or a Ci - C ₂ o- carbon-containing group, of which two or more can form a cyclic system with each other, and X ¹ is hydrogen or a C ₁ -C 20 -carbon-containing group or

Is halogen, and X ² is hydrogen or a C ₁ -C ₂ 0 carbon-containing group or

Is halogen, and m is either 0, 1, 2 or 3, and n is either 0, 1, 2 or 3, and o is either 0, 1, 2 or 3, and p is either 0, 1, 2 or 3 , and the sum of m, n, o and p is always equal to four.

In the context of the present invention, the radicals C ₁ -C ₂₀ -alkyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, are preferably selected from C 1 -C ₂₀ -carbon-containing groups. s-butyl, t-butyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl or cyclooctyl, C ₁ -C 20 -alkenyl, more preferably ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, Hexenyl, cyclohexenyl, octenyl or cyclooctenyl, Ci - C ₂ o - alkynyl, particularly preferred

Ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl, C ₆ -C ₂₀ aryl, more preferably benzylidene, o-methoxybenzylidene, 2,6-dimethylbenzylidene, phenyl, biphenyl, naphthyl, anthracenyl, triphenylenyl, [1, 1 '; 3 ', 1 "] terphenyl-2'-yl, binaphthyl or phenanthrenyl, Ci - C ₂₀ - fluoroalkyl, particularly preferably trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl, C ₆ -C ₂₀ fluoroaryl, particularly preferred

Pentafluorophenyl, 3,5-bistrifluoromethylphenyl, pentafluorobenzylidene, 3,5-bistrifluoromethylbenzylidene, tetrafluorophenyl or heptafluoronaphthyl, C ₁ -C ₂₀ -alkoxy, more preferably methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy, C ₆ -C ₂₀ -aryloxy, particularly preferably phenoxy, Naphthoxy, biphenyloxy, anthracenyloxy, phenanthrenyloxy, C ₇ -C ₂ o-arylalkyl, more preferably o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-i -propylphenyl, 2,6-di-t-butylphenyl, ot-butylphenyl, mt-butylphenyl, pt-butylphenyl, C ₇ -C ₂ o-alkylaryl, more preferably benzyl, ethylphenyl, propylphenyl, diphenylmethyl, triphenylmethyl or naphthalenylmethyl, C ₇ C ₂ o-Aryloxyalkyl, particularly preferably o-methoxyphenyl, m-phenoxymethyl, p-phenoxymethyl, C ₁₂ -C ₂ o-Aryloxyaryl, particularly preferably p-phenoxyphenyl, C ₅ -C ₂ o-heteroaryl, particularly preferably 2-pyridyl , 3-pyridyl, A- pyridyl, quinolinyl, isoquinolinyl, acridinyl, or Benzochinolinyl Benzoisochinolinyl, C ₄ -C ₂ o-heterocycloalkyl, more preferably furyl, benzofuryl, 2-pyrrolidinyl, 2-indolyl, 3-indolyl, 2,3- Dihydroindolyl, C ₈ -C ₂ o-arylalkenyl, particularly preferably o-vinylphenyl, m-vinylphenyl, p-vinylphenyl, C ₈ -C ₂ o-arylalkynyl, particularly preferably o-ethynylphenyl, m-ethynylphenyl nyl or p-ethynylphenyl, C ₂ - C ₂ o - understood heteroatom-containing group, particularly preferably carbonyl, benzoyl, oxybenzoyl, benzoyloxy, acetyl, acetoxy or nitrile, wherein one or more Ci-C ₂ o-carbon-containing groups can form a cyclic system ,

Particular preference is given to compounds of the formula II

Formula Il

wherein: M ^{1 represents} a transition metal of groups 3 to 6 of the Periodic Table of the Elements whose oxidation state is not equal to zero, and preferably Ti, Zr, Hf, V, Mo, Sc, Y, Cr and Nb, and

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^{17 are} each the same or different and equal to hydrogen or a halogen atom or a Ci - C ₂₀ - carbon-containing

Group, which can form two or more among each other a cyclic system, and R ^18, R ^19, R ^20, R ^21, R ^22, R ^23, R ²⁴ are identical or different and each is equal to

Hydrogen or a halogen atom or a Ci - C ₂ o carbon-containing group of which, two or more may form a cyclic system with each other, and X ¹ is hydrogen or a Ci - C ₂₀ - carbon-containing group or a

Is halogen, and

X ² is hydrogen or a C ₁ -C 20 carbon-containing group or a halogen atom, and m is either 0, 1 or 2, and n is either 0, 1 or 2 and 0 is either 0, 1 or 2, and p is either 0, 1 or 2, and the sum of m, n, o and p is always equal to four.

Very particular preference is given to compounds of the formula III

Formula III

wherein:

M ^{1 is} a transition metal of Group 4 of the Periodic Table of the Elements whose oxidation state is not zero, and preferably Ti or Zr, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ are the same or are different and the same

Is hydrogen or a halogen atom or a C 1 -C 20 -carbon-containing compound

Group are two or more of which can form a cyclic system with each other, and X ¹ is hydrogen or a Ci - C ₂ o- carbon-containing group or a

Is halogen, and X ² is hydrogen or a C ₁ -C ₂ 0 carbon-containing group or

Is halogen.

Illustrative but nonlimiting examples of compounds of formulas I-III are:

(2-isopropyl-4- (p-isopropylphenyl) indenyl) (2-methyl-4- (p-isopropylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2-methyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride, (2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2,7-dimethyl-4-p (tert-butylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2,5,6,7-tetramethyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride, (2- isopropyl 6-methyl-4- (p-tert-butylphenyl) indenyl) (2,6-dimethyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-sec.-butylphenyl) indenyl) (2-methyl-4- (p-sec.butylphenyl) indenyl) zirconium dichloride.

(2-isopropyl-4- (p-cyclohexylphenyl) indenyl) (2-methyl-4- (p-cyclohexylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-trimethylsilylphenyl) indenyl) (2-methyl-4- (p-trimethylsilylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-adamantyl-phenyl) indenyl) (2-methyl-4- (p-adamantyl-phenyl) indenyl) -zirconium dichloride, (2-isopropyl-4- (p-tris (trifluoromethyl) -methyl -phenyl) indenyl) (2-methyl-4- (p-tris (trifluoromethyl) methyl-phenyl) indenyl) -zirconium dichloride,

(2-isopropyl-4-phenyl-indenyl) (2-methyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2-methyl-4-phenylindenyl) zirconium dichloride,

(2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2,7-dimethyl-4-phenylindenyl) zirconium dichloride,

(2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2,5,6,7-tetramethyl-4-phenyl-indenyl) zirconium dichloride, (2-isopropyl-6-methyl-4-) (p-tert-butylphenyl) indenyl) (2,6-dimethyl-4-phenyl-indenyl) zirconium dichloride,

(2-isopropyl-4-phenylindenyl) (2,7-dimethyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4-phenylindenyl) (2,5,6,7-tetramethyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-6-methyl-4-phenylindenyl) (2,6-dimethyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride,

(2-isopropyl-4- (p-tert-butylphenyl) indenyl) (2-methyl-4- (4-naphthyl) indenyl) indenyl) zirconium dichloride, (2-isopropyl-4- (4-naphthyl) indenyl) indenyl) (2-methyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride,

Bis (4-naphthyl-indenyl) zirconium dichloride,

Bis (2-methyl- [4,5] -benzo-indenyl) zirconium dichloride bis (2-methyl-indenyl) zirconium dichloride,

Bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride,

Bis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride,

Bis (2-methyl-4-phenyl-indenyl) zirconium dichloride,

Bis (2-methyl-4-tert-butyl-indenyl) zirconium dichloride, bis (2-methyl-4-isopropylindenyl) zirconium dichloride,

Bis (2-methyl-4-ethyl-indenyl) zirconium dichloride,

Bis (2-methyl-4-acenaphth-indenyl) zirconium dichloride,

Bis (2,4-dimethyl-indenyl) zirconium dichloride,

Bis (2-ethyl-indenyl) zirconium dichloride, bis (2-ethyl-4-ethyl-indenyl) zirconium dichloride,

Bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride,

Bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride,

Bis (2-methyl-4,5-diisopropyl-indenyl) zirconium dichloride,

Bis (2,4,6-trimethyl-indenyl) zirconium dichloride, bis (2 _I 5,6-trimethyl-indenyl) zirconium dichloride,

Bis (2,4,7-trimethyl-indenyl) zirconium dichloride,

Bis (2-methyl-5-isobutyl-indenyl) zirconium dichloride,

Bis (2-methyl-5-t-butyl-indenyl) zirconium dichloride,

Bis (2-methyl-4- (tert -butyl-phenyl) -indenyl) zirconium dichloride, bis (2-methyl-4- (4-methylphenyl) -indenyl) zirconium dichloride,

Bis (2-methyl-4- (4-ethyl-phenyl) indenyl) zirconium dichloride,

Bis (2-methyl-4- (4-trifluoromethyl-phenyl) indenyl) zirconium dichloride,

Bis (2-methyl-4- (4-methoxy-phenyl) indenyl) zirconium dichloride,

Bis (2-ethyl-4- (4-tert-butyl-phenyl) -indenyl) zirconium dichloride, bis (2-ethyl-4- (4-methylphenyl) -indenyl) zirconium dichloride,

Bis (2-ethyl-4- (4-ethyl-phenyl) indenyl) zirconium dichloride,

Bis (2-6thyl-4- (4-trifluoromethyl-phenyl) indenyl) zirconium dichloride,

Bis (2-ethyl-4- (4-methoxy-phenyl) indenyl) zirconium dichloride,

Bis (2-methyl-4- (4-tert-butyl-phenyl) indenyl) zirconium dimethyl, Bis (2-methyl-4- (4-methyl-phenyl) indenyl) zirconium dimethyl,

Bis (2-methyl-4- (4-ethylphenyl) -indenyl) zirconium dimethyl, bis (2-methyl-4- (4-trifluoromethylphenyl) -indenyl) zirconium dimethyl, bis (2-methyl-4- (4 -methoxy-phenyl) -indenyl) zirconium dimethyl, bis (2-ethyl-4- (4-tert-butyl-phenyl) -indenyl) zirconium-dimethyl,

Bis (2-ethyl-4- (4-methylphenyl) -indenyl) zirconium dimethyl, bis (2-ethyl-4- (4-ethylphenyl) -indenyl) zirconium dimethyl, bis (2-ethyl-4- (4 -trifluoromethylphenyl) indenyl) zirconium dimethyl, bis (2-ethyl-4- (4-methoxyphenyl) indenyl) zirconium dimethyl, bis (2-isopropyl-4- (tert -butylphenyl) indenyl) zirconium dichloride,

Bis (2-isopropyl-4- (4-methyl-phenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4-ethylphenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4 -trifluoromethyl-phenyl) indenyl) zirconium dichloride, bis (2-isopropyl-4- (4-methoxy-phenyl) indenyl) zirconium dichloride, bis (2-isopropyl-4- (4 ^{'-tert-butyl-phenyl)} - indenyl) zirconium dichloride,

Bis (2-isopropyl-4- (4 ^{'-tert-butyl-phenyl)} -indeny!) Hafnium dichloride, bis (2-isopropyl-4- ^(4' -tert-butyl-phenyl) indenyl) titanium dichloride, bis (2-isopropyl-4- (4 ^{'-methyl-phenyl)} -indenyl) zirconium dichloride, bis (2-isopropyl-4- ^(4' -n-propyl-phenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4 - (4 ^{'-n-butyl-phenyl)} indenyl) zirconium dichloride,

Bis (2-isopropyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4 ^{'-sec-butyl-phenyl)} indenyl) zirconium dichloride, bis (2-isopropyl- 4-phenyl) indenyl) zirconium dichloride, bis (2-isopropyl4- (4'-methyl-phenyl) indenyl) zirconium dichloride, bis (2-isopropyl-4- (4 ^{'-ethyl-phenyl)} -indenyl) zirconium dichloride,

Bis (2-isopropyl-4- (4 ^{'-n-propyl-phenyl)} -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride, bis (2- isopropyl 4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4'-pentyl-phenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4 ^' -) cyclohexyl-phenyl) indenyl) zirconium dichloride,

Bis (2-isopropyl-4- (4'-sec-butyl-phenyl) -indenyl) zirconium dichloride, bis (2-isopropyl-4- (4'-tert-butyl-phenyl) -indenyl) zirconium dichloride, bis (2 -methyl-4- (4'-tert-butyl-phenyl) -indenyl) zirconium dichloride, bis (2-methyl-4- (4'-tert-butylphenyl) -indenyl) hafnium dichloride, Bis (2-methyl-4- (4 ^{'-tert-butyl-phenyl)} indenyl) titanium dichloride,

Bis (2-methyl-4- (4'-methyl-phenyl) -indenyl) zirconium dichloride, bis (2-methyl-4- (4'-n-propyl-phenyl) -indenyl) zirconium dichloride, bis (2-methyl 4- (4'-n-butylphenyl) indenyl) zirconium dichloride, bis (2-methyl-4- (4'-hexylphenyl) -indenyl) zirconium dichloride,

Bis (2-methyl-4- (4 ^{'-sec-butyl-phenyl)} indenyl) zirconium dichloride, bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride, bis (2-ethyl-4- ^(4' -methyl phenyl) indenyl) zirconium dichloride, bis (2-ethyl-4- (4'-ethyl-phenyl) indenyl) zirconium dichloride, bis (2-ethyl-4- (4 ^{'-n-propyl-phenyl)} -indenyl) zirconium,

Bis (2-ethyl-4- (4 ^{'-n-butyl-phenyl)} indenyl) zirconium dichloride, bis (2-ethyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride, bis (2-ethyl- 4- (4'-pentyl-phenyl) -indenyl) zirconium dichloride, bis (2-ethyl-4- (4'-cyclohexylphenyl) -indenyl) zirconium dichloride, bis (2-ethyl-4- (4'-sec-butyl) butyl-phenyl) indenyl) zirconium dichloride,

Bis (2-ethyl-4- (4 ^{'-tert-butyl-phenyl)} indenyl) zirconium dichloride, bis (2-n-propyl-4-phenyl-indenyl) zirconium dichloride, bis (2-n-propyl-4- (4 ^{'-methyl-phenyl)} -indenyl) zirconium dichloride, bis (2-n-propyl-4- ^(4' -ethyl-phenyl) -indenyl) zirconium dichloride, bis (2-n-propyl-4- (4 ^'- iso-propyl-phenyl) -indenyl) zirconium dichloride,

Bis (2-n-propyl-4- (4'-n-butylphenyl) indenyl) zirconium dichloride, bis (2-n-propyl-4- (4'-hexylphenyl) indenyl) zirconium dichloride, bis ( 2-n-propyl-4- (4 ^{'-cyclohexyl-phenyl)} -indenyl) zirconium dichloride, bis (2-n-propyl-4- ^(4' -sec-butyl-phenyl) indenyl) zirconium dichloride, bis (2- n-propyl-4- (4 ^{'-tert-butyl-phenyl)} indenyl) zirconium dichloride,

Bis (2-n-butyl-4-phenylindenyl) zirconium dichloride, bis (2-n-butyl-4- (4'-methyl-phenyl) -indenyl) zirconium dichloride, bis (2-n-butyl-4-) (4'-ethyl-phenyl) -indenyl) zirconium dichloride, bis (2-n-butyl-4- (4'-n-propyl-phenyl) -indenyl) zirconium dichloride, bis (2-n-butyl-4- ( 4'-iso-propyl-phenyl) -indenyl) zirconium dichloride,

Bis (2-n-butyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride, bis (2-n-butyl-4- (4 ^{'-hexyl-phenyl)} -indenyl) zirconium dichloride, bis ( 2-n-butyl-4- (4'-cyclohexylphenyl) indenyl) zirconium dichloride, bis (2-n-butyl-4- (4'-sec-butyl-phenyl) -indenyl) zirconium dichloride, Bis (2-n-butyl-4- (4 ^{'-tert-butyl-phenyl)} indenyl) zirconium dichloride,

Bis (2-hexyl-4-phenyl-indenyl) zirconium dichloride,

Bis (2-hexyl-4- (4 ^{'-methyl-phenyl)} -indenyl) zirconium dichloride,

Bis (2-hexyl-4- (4 ^{'-ethyl-phenyl)} -indenyl) zirconium dichloride, bis (2-hexyl-4- ^(4' -n-propyl-phenyl) -indenyl) zirconium dichloride,

Bis (2-hexyl-4- (4 ^{'-iso-propyl-phenyl)} -indenyl) zirconium dichloride, bis (2-hexyl-4- ^(4' -n-butyl-phenyl) - indenyl) zirconium dichloride, bis (2 -hexyl-4- (4 ^{'-n-hexyl-phenyl)} -indenyl) zirconium dichloride, bis (2-hexyl-4- ^(4' -cyclohexyl-phenyl) -indenyl) zirconium dichloride, bis (2-hexyl-4- ( 4 ^{'-sec-butyl-phenyl)} indenyl) zirconium dichloride,

Bis (2-hexyl-4- (4 ^{'-tert-butyl-phenyl)} indenyl) zirconium dichloride, bis (2-phenyl-4-phenyl-indenyl) zirconium dichloride, bis (2-phenyl-4- ^(4' - methyl-phenyl) indenyl) zirconium dichloride, bis (2-phenyl-4- (4 ^{'-ethyl-phenyl)} -indenyl) zirconium dichloride, bis (2-phenyl-4- (4'-n-propyl-phenyl) -indenyl ) zirconium,

Bis (2-phenyl-4- (4 ^{'-iso-propyl-phenyl)} -indenyl) zirconium dichloride, bis (2-phenyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride, bis (2- phenyl-4- (4 ^{'-n-hexyl-phenyl)} -indenyl) zirconium dichloride, bis (2-phenyl-4- ^(4' -cyclohexyl-phenyl) -indenyl) zirconium dichloride, bis (2-phenyl-4- (4 ^' -sec-butyl-phenyl) -indenyl) zirconium dichloride,

Bis (2-phenyl-4- (4 ^' - tert -butyl-phenyl) -indenyl) zirconium dichloride, bis (2-methyl-4- (4 ^' - tert -butyl-phenyl) -indenyl) zirconium bis (dimethylamines) , bis (2-ethyl-4- (4 ^{'-tert-butyl-phenyl)} indenyl) zirconium dibenzyl, bis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dimethyl, ( 2-methyl-4-azapentalene) (2-methyl-4- (4 ^{'-methyl-phenyl)} -indenyl) zirconium dichloride,

(2-methyl-5-azapentalene) (2-methyl-4- (4 ^{'-methyl-phenyl)} -indenyl) zirconium dichloride, (2-methyl-6-azapentalene) (2-methyl-4- ^(4' -methyl -phenyl) -indenyl) zirconium dichloride, (2-methyl-4-azapentalene) (2-methyl-4- (4'-ethylphenyl) -indenyl) zirconium dichloride, (2-methyl-4-thiapentalene) (2-methyl -4- (4'-n-propyl-phenyl) -indenyl) zirconium dichloride, (2-methyl-4-azapentalene) (2-methyl-4- (4'-isopropylphenyl) -indenyl) zirconium dichloride,

(2-methyl-6-azapentalene) (2-methyl-4- (4'-isopropylphenyl) -indenyl) zirconium dichloride, (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 ^{'-isopropyl-phenyl)} -indenyl) - zirconiumdichloride,

(2-methyl-6-oxapentalen) (2-methyl-4- (4 ^{'-isopropyl-phenyl)} -indenyl) zirconium dichloride, (2-methyl-6-azapentalene) (2-methyl-4- ^(4' -n -butyl-phenyl) -indenyl) zirconium dichloride,

(2-methyl-5-thiapentalene) (2-methyl-4- (4 ^{'-n-butyl-phenyl)} indenyl) zirconium dichloride,

(2-methyl-4-oxapentalen) (2-methyl-4- (4 ^{'-n-butyl-phenyl)} indenyl) zirconium dichloride,

(2-methyl-4-thiapental) (2-methyl-4- (4'-s-butyl-phenyl) -indenyl) zirconium dichloride,

(2-methyl-4-oxapentalene) (2-methyl-4- (4 ^' -s-butyl-phenyl) -indenyl) zirconium dichloride, (2-methyl-4-azapentalene) (2-methyl-4- (4' tert-butylphenyl) indenyl) zirconium dichloride,

(2-methyl-6-azapentalene) (2-methyl-4- (4'-tert-butylphenyl) -indenyl) zirconium dichloride,

(2-methyl-4-azapentalene) (2-methyl-4- (4 ^{'-n-pentyl-phenyl)} -indenyl) - zirconiumdichloride,

(2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4'-n-pentylphenyl) -indenyl) zirconium dichloride,

(2-methyl-4-oxapentalen) (2-methyl-4- (4'-n-pentyl-phenyl) -indenyl) zirconium dichloride,

(2-methyl-4-azapentalene) (2-methyl-4- (4'-n-hexyl-phenyl) -indenyl) zirconium dichloride, (2-methyl-4-thiapentalene) (2-methyl-4- (4 ^' -n-hexyl-phenyl) -indenyl) zirconium dichloride,

(2-methyl-6-thiapentalene) (2-methyl-4- (4'-n-hexyl-phenyl) -indenyl) zirconium dichloride,

(2,5-dimethyl-4-thiapental) (2-methyl-4- (4'-n-hexylphenyl) -indenyl) zirconium dichloride,

(2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4 ^{'-n-hexyl-phenyl)} -indenyl) - zirconiumdichloride,

(2,5-dimethyl-6-thiapental) (2-methyl-4- (4'-cyclohexyl-phenyl) -indenyl) zirconium dichloride,

(2-methyl-4-azapentalene) (2-methyl-4- (4'-trimethylsilylphenyl) indenyl) zirconium dichloride, (2-methyl-4-thiapentalene) (2-methyl-4- (4'-methyl) trimethylsilylphenyl) indenyl) zirconium dichloride,

(2-methyl-5-thiapental) (2-methyl-4- (4'-trimethylsilylphenyl) indenyl) zirconium dichloride, (2-methyl-6-thiapental) (2-methyl-4- (4'-trimethylsilyl-2-phenyl) -indenyl) -zirconium dichloride,

(2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-adamantyl-phenyl) -indenyl) -zirconium dichloride, (2-methyl-4-thiapentalene) (2-methyl-4- (4 ^' -adamanty! -phenyl) -indenyl) - zirconium dichloride,

(2-methyl-6-thiapentalene) (2-methyl-4- (4 ^{'-adamantyl-phenyl)} -indenyl!) - zirconium dichloride,

(2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4 ^{'-adamantyl-phenyl)} -indenyl) - zirconiumdichloride,

(2-methyl-4-azapentalene) (2-methyl-4- (4 ^' -tris (trifluoromethyl) methylphenyl) -indenyl) zirconium dichloride,

(2,5-dimethyl-4-azapentalene) (2-methyl-4- (4'-tris (trifluoromethyl) methyl-phenyl) -indenyl) -zirconium dichloride, (2-methyl-4-thiapentalene) 4- (4 ^'-tris (trifluoromethyl) methyl-phenyl) indenyl) - zirconium dichloride,

(2-methyl-6-thiapental) (2-methyl-4- (4 ^' - tris (trifluoromethyl) methylphenyl) indenyl) zirconium dichloride,

(2-methyl-4-azapentalene) (2-ethyl-4- (4 ^' - tert -butyl-phenyl) -indenyl) zirconium dichloride, (2-methyl-5-azapentalene) (2-n-butyl-4-) (4'-tert-butylphenyl) indenyl) zirconium dichloride,

(2-methyl-N-phenyl-6-azapentalene) (2-methyl-4- (4 ^{'-tert-butyl-phenyl)} -indenyl) ~ zirconiumdichloride,

(2-methyl-4-azapenta! En) (2-methylindenyl) zirconium dichloride, (2-methyl-N-phenyl-4-azapentalene) (2-methylindenyl) zirconium dichloride,

(2-methyl-4-thiapentalene) (2-methylindenyl) zirconium dichloride,

(2-methyl-5-thiapentalene) (2-methylindenyl) zirconium dichloride,

(2-methyl-6-thiapentalene) (2-methylindenyl) zirconium dichloride,

(2-methyl-4-azapentalene) (indenyl) zirconium dichloride, (2-methyl-5-azapentalene) (indenyl) zirconium dichloride,

(2-methyl-6-azapentalene) (indenyl) zirconium dichloride,

(2-methyl-N-phenyl-4-azapentalene) (indenyl) zirconium dichloride,

(2-methyl-N-phenyl-5-azapentalene) (indenyl) zirconium dichloride,

(2-methyl-N-phenyl-6-azapentalene) (indenyl) zirconium dichloride, (2,5-dimethyl-N-phenyl-6-azapentalene) (indenyl) zirconium dichloride,

(2-methyl-4-thiapental) (indenyl) zirconium dichloride, (2-methyl-5-thiapentalene) (indenyl) zirconium dichloride, (2-methyl-6-thiapentalene) (indenyl) zirconium dichloride, (2,5-dimethyl-4 thiapental) (indenyl) zirconium dichloride,

(2-methyl-4-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-5-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-6 ~ azapental) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-N-phenyl-4-azapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-N-phenyl -5-azapentalene) (2-methyl-4-phenyl-indenyl) zirconium dichloride,

(2-methyl-4-thiapental) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-5-thiapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-6 thiapental) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-4-oxapentalene) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methyl-4-azapentalene) (2- methyl-4,5-benzo-indenyl) zirconium dichloride,

(2-methyl-N-phenyl-4-azapentalene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, (2-methyl-N-phenyl-5-azapentalene) (2-methyl-4,5- benzo-indenyl) zirconium dichloride, (2-methyl-N-phenyl-6-azapentalene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, (2-methyl-4-thiapentalene) (2-methyl-4, 5-benzo-indenyl) zirconium dichloride, (2-methyl-5-thiapentalene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride,

(2-methyl-6-thiapental) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, (2-methyl-4-oxapentalene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, (2 -methyl-5-oxapentalene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, (2-methyl-6-oxapentalene) (2-methyl-4,5-benzo-indenyl) zirconium dichloride, bis (2-methyl-4-oxapentalene) methyl-4-azapentalene) zirconium dichloride,

Bis (2-methyl-N-phenyl-4-azapentalene) zirconium dichloride, bis (2-methyl-4-thiapental) zirconium dichloride,

and the corresponding titanium and hafnium compounds.

The synthesis of the compounds of the formula I according to the invention can be carried out by processes known to the person skilled in the art (cf., EP97. An example of this is listed below.

The compounds of the formula I according to the invention are particularly suitable as constituents of catalyst systems for the preparation of polyolefins by polymerization of at least one olefin in the presence of a catalyst which comprises at least one cocatalyst and at least one compound according to the invention.

Another component of the present invention is a process for the polymerization of ethylene using the invention

Catalysts, polymerization being understood to mean both the homopolymerization of ethylene and the copolymerization of ethylene with other olefins. Examples of other olefins are 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-olefin. Octene, styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinylnorbornene,

Norbornadiene, ethylnorbornadiene and cyclic olefins such as norbornene, cyclopentadiene, tetracyclododecene or methylnorbomene. In the process according to the invention, ethylene is preferably homopolymerized, or ethylene is copolymerized with one or more 1-olefins having 2 to 8 C atoms, such as propene, 1-butene, 1-pentene, 1-hexene, styrene, norbornene or butadiene.

The polymerization is preferably at a temperature from -20 to 300 ⁰ C ₁ 0 to 200 ⁰ C, most preferably at 20 to 100 ⁰ C performed. The pressure is 0.5 to 2000 bar, preferably 1 to 64 bar. The polymerization can be in solution, in

Mass, in suspension or in emulsion, continuously or discontinuously, be carried out in one or more stages.

Suitable solvents for the polymerization are, for example, aliphatic hydrocarbons such as pentane, hexane and the like or aromatic

Hydrocarbons such as benzene, toluene, xylene and the like, or ethers such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether and ethyl phenyl ether, also halogenated solvents such as dichloromethane, trichloromethane, chlorobenzene, bromobenzene and the like. It can also mixtures of different solvents in different

Quantity ratios are used according to the invention.

The present invention further provides catalyst systems for the preparation of polyolefins by polymerization of at least one olefin in the presence of at least one compound of the formula I. These catalyst systems comprise, in addition to at least one compound of the formula I, at least one cocatalyst.

The cocatalyst which forms the catalyst system together with at least one transition metal compound of the formula I contains at least one compound from

Type of an aluminoxane or a Lewis acid or an ionic compound which, by reaction with the transition metal compound, converts them into a cationic compound.

As aluminoxane is preferably a compound of general formula IV

(R AIO) q

Formula IV used.

Other suitable aluminoxanes may be e.g. cyclic as in formula V.

+ 2 Formula V

or linear as in formula VI

Formula VI

or of the cluster type as in formula VII

R

Be formula VII. Such aluminoxanes are described, for example, in JACS 1 17 (1995), 6465-74, Organometallics 13 (1994), 2957-2969.

The radicals R in the formulas IV, V, VI and VII may be the same or different and represent a C ^<| C20 hydrocarbon group such as a Ci-Css alkyl group, a CSS

C 1-8 aryl group, benzyl or hydrogen, and q is an integer from 2 to

50, preferably 10 to 35 mean.

Preferably, the radicals R are the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl. If the radicals R are different, then they are preferably methyl and hydrogen,

Methyl and isobutyl or methyl and n-butyl, wherein hydrogen or isobutyl or n-butyl preferably to 0.01 - 40% (number of radicals R) are included. The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, that an aluminum hydrocarbon compound and / or a Hydridoaluminium- hydrocarbon compound with water (gaseous, solid, liquid or bound - for example, as water of crystallization) in an inert solvent (such as toluene) is reacted.

To prepare an aluminoxane having different alkyl groups R, two different trialkylaluminums (AIR3 + AIR'3) are reacted with water according to the desired composition and reactivity (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A-0, 302,424). ,

Regardless of the manner of preparation, all aluminoxane solutions have in common an alternating content of unreacted starting aluminum compound which is in free form or as an adduct.

The preferred Lewis acid is at least one borane or organoaluminum compound containing C 1 -C 20 carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, e.g. Methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, ToIyI, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl,

Pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di (trifluoromethyl) phenyl.

Examples of Lewis acids are trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,

Tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (tolyl) borane, tris (3,5-dimethylphenyl) borane, tris ( 3,5-difluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Particularly preferred is tris (pentafluorophenyl) borane.

As ionic cocatalysts it is preferred to use compounds which contain a non-coordinating anion, for example Tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF ", CF3SO3 or CIO4-.

As a cationic counterion protonated Lewis bases such as methylamine, aniline, N, N-dimethylbenzylamine and their derivatives, N ₁ N-dimethylcyclohexylamine and their derivatives, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, Triethylamine, tri-n-butylamine,

Methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene or triphenylcarbenium used.

Examples of such ionic compounds are

Triethylammonium tetra (phenyl) borate,

Tributylammoniumtetra (phenyl) borate,

Trimethylammoniumtetra (tolyl) borate,

Tributylammonium tetra (tolyl) borate, tributylammonium tetra (pentafluorophenyl) borate,

Tributylammonium tetra (pentafluorophenyl) aluminate,

Tripropylammoniumtetra (dimethylphenyl) borate,

Tributylammoniumtetra (trifluoromethylphenyl) borate,

Tributylammonium tetra (4-fluorophenyl) borate, N, N-dimethylanilinium tetra (phenyl) borate,

N, N-Diethylaniiiniumtetra (phenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate,

Di (propyl) ammonium tetrakis (pentafluorophenyl) borate, di (cyclohexyl) ammonium tetrakis (pentafluorophenyl) borate,

Triphenylphosphonium tetrakis (phenyl) borate,

Triethylphosphoniumtetrakis (phenyl) borate,

N, N-Dimethylcyclohexylammoniumtetrakis (pentafluorophenyl) borate

N, N-dimethylbenzylammonium tetrakis (pentafluorophenyl) borate diphenylphosphonium tetrakis (phenyl) borate,

Tri (methylphenyl) phosphoniumtetrakis (phenyl) borate,

Tri (dimethyl phenyl) phosphonium (phenyl) borate,

Triphenylcarbenium tetrakis (pentafluorophenyl) borate, Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,

Triphenylcarbenium tetrakis (phenyl) aluminate, ferrocenium tetrakis (pentafluorophenyl) borate and / or ferrocenium tetrakis (pentafluorophenyl) aluminate. Preference is TriphenylcarbeniumtetrakisφentafluorophenyOborat and / or

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

It is also possible to use mixtures of at least one Lewis acid and at least one ionic compound.

As co-catalyst components are also borane or carborane compounds such as e.g.

7,8-dicarbaundecaborane (13),

Undecahydride-T.δ-dimethyl-T.δ-dicarbaundecaborane,

Dodecahydride-1-phenyl-1,3-dicarbanonaboran, tri (butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate,

4-carbanonaborane (14) bis (tri (butyl) ammonium) nonaborate,

Bis (tri (butyl) ammonium) undecaborate,

Bis (tri (butyl) ammonium) dodecaborate

Bis (tri (butyl) ammonium) decachlorodecaborate, tri (butyl) ammonium 1 -carbadecaborate,

Tri (butyl) ammonium-1-carbadodecaborate,

Tri (butyl) ammonium-1-trimethylsilyl-1-carbadecaborate,

Tri (buyl) ammonium bis (nonahydride-1,3-dicarbonnonaborate) cobaltate (III),

Tri (butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III).

Also suitable as cocatalyst systems are combinations of at least one of the abovementioned amines and optionally a carrier with organometallic compounds as described in patent WO 99/40129. The carriers mentioned in WO 99/40129 with organometallic compounds are likewise part of the present invention.

Preferred constituents of these cocatalyst systems are the compounds of the formulas A and B, Formula A

Formula B wherein

R ₅ 25 represents a hydrogen atom, a halogen atom, a Ci-C ₂₀ carbon-containing

Group, in particular dC ₂ o-alkyl, dC ₁ -haloalkyl, C ₁ -C 10 -alkoxy, C ₆ -cano-aryl, C ₆ -C ₂ _0- haloaryl, C ₆ -C ₂ o-aryloxy, C ₇ - C ₂ o-arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₂ Q-alkylaryl or C ₇ -C ₂₀ -haloalkylaryl. R ²⁵ may also be an -OSiR ₃ group, wherein R is the same or different and has the same meaning as R ²⁵ .

In addition, compounds which are obtained by the reaction of at least one compound of the formula C and / or D and / or E with at least one compound of the formula F are generally to be regarded as a further preferred cocatalyst.

R _f ²⁶ B- (LR ²⁵ ) _g Formula C

R ₂ ²⁵ BX ³ -BR ₂ ²⁵ Formula D

Formula E Formula F wherein

R j25 has the same meaning as mentioned above, and R ^{26 is} a hydrogen atom or a boron-free C 1 -C 4 -carbon-containing group, such as

C- ₂₀ alkyl, C ₆ -C ₂ o-aryl, C ₇ -C ₂₀ arylalky, C ₇ -C ₂ o-alkylaryl and X ^{3 may be} an element of the 16th group of the Periodic Table of the Elements or an NR group wherein R is o-hydrocarbon radical such as CiC ₂ o alkyl or CiC ₂ is a hydrogen atom or a Ci ~ _C2o-aryl, and L is equal to an element of the 16th group of the Periodic Table of the elements or an NR group, wherein R is a hydrogen atom or a Ci-C ₂₀ - hydrocarbon radical such as Ci-C ₂₀ alkyl or CrC ₂ o-aryl, f is an integer from 0 to 3, g is an integer from 0 to 3, where z + y are not 0, h is an integer of 1 to 10.

Optionally, the organometallic compounds are combined with an organometallic compound of the formula IV to VII and or VIII [M2R27 ₍ .) | _< Wherein M ^ is an element of the 1st, 2nd and 13th group of the Periodic Table of the Elements, R27 are the same or different is and a hydrogen atom, a halogen atom, a

C1-C40-carbon-containing group, in particular C1-C20-alkyl, C3-C15-aryl, C7-C20-aryl-alkyl or C7-C20-alkyl-aryl group, r is a whole Number of 1 to 3 and k is an integer of 1 to 4.

Examples of the cocatalytically active compounds of the formulas A and B are

H ₀ C-AI-OBO-AI-CH "3,

CH, CH,

The organometallic compounds of the formula F are preferably neutral Lewis acids in which M is lithium, magnesium and / or aluminum, in particular aluminum. Examples of the preferred organometallic compounds of the formula F are trimethylaluminum, triethylaluminum, trisodium isopropylaluminum, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisoprenaluminum, dimethylaluminum monochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum sesqui chloride, ethylaluminum sesquichloride, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, dimethylaluminum (trimethylsiloxide), dimethylaluminum (triethylsiloxide), phenylalan, pentafluorophenylalan and o-tolylalan.

Further cocatalysts which may be unsupported or supported are those described in EP-A-924223, DE-A-19622207, EP-A-601830, EP-A-824112, EP-A-824113, EP-A-811627, US Pat. To use WO97 / 11775 and DE-A-19606167.

Furthermore, the catalysts of the invention can be used homogeneously and also heterogeneously supported. The carrier component of the catalyst system may be any organic or inorganic inert

Solid, especially a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g., polyolefins).

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 the carrier include silica, alumina and mixed oxides of the elements calcium,

Aluminum, silicon, magnesium, titanium and corresponding oxide mixtures, as well as hydrotalcites. Other inorganic oxides which can be used alone or in combination with the last-mentioned preferred oxide supports are, for example, MgO, ZrO ₂ , TiO ₂ or B ₂ O ₃ , to name only a few. The support materials used have a specific surface area in the range of 10 to 1000 m ² / g, a pore volume in the range of 0.1 to 5 ml / g and an average particle size of 1 to 500 microns. Preference is given to carriers having a specific surface area in the range from 50 to 500 μm, 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. Particular preference is given to supports having a specific surface area in the

Range of 200 to 400 m ² / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 microns. If the support material used is inherently low in moisture content or residual solvent content, dehydration may occur or avoid drying before use. If this is not the case, as with the use of silica gel as a carrier material, dehydration or drying is recommended. The thermal dehydration or drying of the support material can be carried out under vacuum and simultaneous inert gas overlay (eg nitrogen). The drying temperature is in the range between 100 and

1000 ^° C., preferably between 200 and 800 ^° C. The parameter pressure is not decisive in this case. The duration of the drying process can be between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the conditions chosen, equilibration can be achieved with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.

Dehydration or drying of the support material is also chemically possible by reacting the adsorbed water and hydroxyl groups on the surface with suitable inerting agents. By reaction with the inerting reagent, the hydroxyl groups can be completely or partially converted into a form which does not lead to a negative interaction with the catalytically active centers. Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane or organometallic compounds of aluminum, boron and magnesium, for example trimethylaluminum, triethylaluminum, triisobutylaluminum, triethylborane, dibutylmagnesium. The chemical dehydration or inertization of the carrier material is carried out, for example, by reacting under air and moisture exclusion a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent for reaction. Suitable solvents include aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene. The inertization is carried out at temperatures between 25 ° C and 120 ⁰ C, preferably between 50 and 70 ⁰ C. Higher and lower temperatures are possible. The duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours. After completion of the chemical dehydration, the support material is isolated by filtration under inert conditions, one or more times with suitable inert solvents as before have been washed and then in inert gas or on

Vacuum dried.

Organic support materials such as finely divided polyolefin powders (e.g., polyethylene, polypropylene, or polystyrene) may also be used, and should also be free from the use of adherent moisture, residual solvents, or others

Impurities are cleaned by appropriate cleaning and drying operations.

To prepare the supported catalyst system, at least one of the compounds of the formula I described above is brought into contact with at least one cocatalyst component in a suitable solvent, preferably a soluble reaction product, an adduct or a mixture being obtained. The resulting formulation is then mixed with the dehydrated or inertized support material, the solvent removed and the resulting supported catalyst system dried to ensure that the solvent is completely or mostly removed from the pores of the support material. The supported catalyst is obtained as a free-flowing powder.

A process for the preparation of a free-flowing and optionally prepolymerized supported catalyst system comprises the following steps: a) preparation of a mixture of at least one compound of formula I and at least one cocatalyst in a suitable solvent or suspending agent, b) application of those obtained from step a) C) removing the majority of solvent from the resulting mixture; d) isolating the supported catalyst system; e) optionally pre-polymerizing the resulting supported catalyst system with one or more olefinic monomer (s) to form a prepolymerized supported To obtain catalyst system.

Preferred solvents in step a) are hydrocarbons and hydrocarbon mixtures which are liquid at the chosen reaction temperature and in which the individual components preferentially dissolve. However, the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of Compound of formula I and cocatalyst is soluble in the chosen solvent.

Examples of suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Very particular preference is given to toluene.

The amounts of aluminoxane and compound of formula I used in the preparation of the supported catalyst system can be varied over a wide range. A molar ratio of aluminum to the transition metal in the compound of the formula I is preferably set from 10: 1 to 1000: 1, very particularly preferably a ratio of from 50: 1 to 500: 1.

In the case of methylaluminoxane, preference is given to using 30% strength toluene solutions; the use of 10% solutions is also possible. For preactivation, the compound of formula I is dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the compound of formula I separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Preferably, toluene is used. The pre-activation time is 1 minute to 200 hours. The preactivation can take place at room temperature (25 ^° C.). The use of higher temperatures can shorten the required duration of pre-activation in individual cases and cause an additional increase in activity. Higher temperature in this case means a range between 50 and 100 ^° C. The preactivated solution or the mixture is subsequently combined with an inert carrier material, usually silica gel, which is present in the form of a dry powder or as a suspension in one of the abovementioned solvents ,

Preferably, the carrier material is used as a powder. The order of addition is arbitrary. The preactivated metallocene cocatalyst solution or the metallocene cocatalyst mixture can be added to the initially introduced carrier material, or else the carrier material can be introduced into the initially introduced solution. The volume of the preactivated solution or of the metallocene

Cocatalyst mixture can exceed 100% of the total pore volume of the carrier material used or up to 100% of the total pore volume. The temperature at which the preactivated solution or the metallocene

Cocatalyst mixture is brought into contact with the carrier material may vary in the range between 0 and 100 ⁰ C. Lower or higher temperatures are also possible. Subsequently, the solvent is completely or for the most part of the supported

Catalyst system removed, wherein the mixture can be stirred and optionally also heated. Preferably, both the visible portion of the solvent and the proportion in the pores of the carrier material is removed. The removal of the solvent can be carried out in a conventional manner using vacuum and / or inert gas purging. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ⁰ C. The free solvent is the visible amount of solvent in the mixture. By residual solvent is meant the portion trapped in the pores. Alternatively to a complete removal of the solvent, the supported

Catalyst system to be dried only to a certain residual solvent content, the free solvent has been completely removed. Subsequently, the supported catalyst system can be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.

The supported catalyst system as illustrated may be used either directly for the polymerization of olefins or prepolymerized prior to its use in a polymerization process with one or more olefinic monomers. The execution of the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.

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 or an antistatic agent (as described in US Serial No. 08 / 365,280) may be added. The molar ratio of additive to metallocene

Component (compound according to formula I) is preferably between 1: 1000 to 1000: 1, most preferably 1: 20 to 20: 1. Another component of the present invention are unbridged catalysts of the formula IX

Formula IX

M ^{1 represents} a transition metal of Group 4 of the Periodic Table of the Elements whose oxidation state is not equal to zero, and preferably Ti or Zr, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²⁸ , R ²⁹ R ³⁰ , R ³¹ are the same or different and are each hydrogen or a halogen atom or a C ₁ -C 20 carbon-containing group, two or more of which may form a cyclic system with one another, and

X ¹ is hydrogen or a C ₁ -C 20 carbon-containing group or a halogen atom, and

X ² is hydrogen or a C ₁ -C 20 -carbon group or a halogen atom. Compounds of the formula IX are very particularly preferably used in the process according to the invention for the preparation of ultrahigh molecular weight polymers.

The invention is illustrated by the following, but not limiting examples of the invention.

General information: The preparation and handling of the organometallic

Compounds were carried out under exclusion of air and moisture under argon protective gas (Schlenk technique or glove box). All required solvents were purged with argon before use and made absolute via molecular sieves.

Example 1 :

Synthesis of bis [2-isopropyl-4- (p-tert-butylphenyl) indenyl] zirconium dichloride 1

In a heated Schlenk tube 3.0 g (10.3 mmol) of 2-isopropyl-4- (p-tert-butylphenyl) inden in 25 ml of abs. Dissolved diethyl ether. Then 4.2 ml (10.5 mmol) of n-butyllithium (2.5 M in toluene) are slowly added with stirring at room temperature. It is stirred for a further hour and then the mixture is heated to 40 ⁰ C for three hours. After cooling to 0 ⁰ C 1.67 g (5.2 mmol) of zirconium tetrachloride-dimethyl ether complex are added and the mixture is stirred for 15 hours at room temperature. Finally, the mixture is again heated to 4O ⁰ C for two hours. The precipitate is filtered off under inert gas and washed well with heptane. The remaining solid is dried under reduced pressure and used further in this form.

Yield: 0.95 g (25%); Mixture: rac / meso 1: 2 rac: ¹ HNMR (500 MHz, C ₆ D ₆ ): δ = 7.48, 7.36 (d, J = 8.4 Hz, 8H, 12-H, 13-H, 15-H , 16-H), 7.35 - 7.20 (m, 6H, 5-H, 6-H, 7-H), 7.18, 6.45 (d, J = 1.4 Hz, 4H ₁ 1 -H, 3-H), 2.48 (sept, J = 6.7 Hz, 2H, 8-H) ₁ 1.27 (s, 18H, 18-H) ₁ 1.00 (d, J = 6.7 Hz, 12H, 9-H, 10-H) ppm. meso: ¹ H-NMR (500 MHz, C ₆ D ₆ ): δ = 7.85, 7.38 (d, J = 8.4 Hz, 8H ₁ 12-H, 13-H, 15-H ₁ 16-H), 7.27 ( d, J = 6.7 Hz, 2H, 5/7-H) ₁ 7.20 (d, J = 8.4 Hz, 2H, 5/7-H) ₁ 6.98 (dd, J = 8.4 / 6.7 Hz, 2H, 6-H ), 6.86, 6.00 (d, J = 2Hz, 4H, 1-H, 3-H), 2.84 (sept, J = 7.0Hz, 2H, 8-H), 1.22 (s, 18H, 18-H) ₁ 1.05, 0.96 (d, J = 7.0 Hz, 12H, 9-H, 10-H) ppm.

Example 2:

Synthesis of bis (2,4,7-trimethylindenyl) zirconium dichloride 2

Procedure analogous to Example 1; Batch size: 5 mmol ZrCl ₄

Yield: 0.70 g (29%); rac-pure rac: ¹ H-NMR (500 MHz, C ₆ D ₆ ): δ = 6.71, 6.14 (s, 4H ₁ 5-H, 6-H), 2.29 (s, 12H, 9-H, 10 H), 1.91 (s, 6H, 8-H) ppm.

Example 3:

Synthesis of bis [2-methyl-4- (p-tert-butylphenyl) indenyl] zirconium dichloride 3 Procedure analogous to Example 1; Batch size: 4.8 mmol ZrCl ₄

Yield: 1.53 g (47%); rac / meso 1: 1.2 rac: ¹ HNMR (500 MHz, C ₆ D ₆ ): δ = 7.72, 7.38 (d, J = 8.7 Hz, 8H, 10-H, 11-H, 13-H ₁ 14 -H), 7.16 (dd, J = 7.0 / 1.0 Hz, 2H, 5/7-H), 7.09 (dd, J = 8.4 / 1.0 Hz ₇ 2H, 5 / 7- H), 6.89 (dd, J = 8.4 / 7.0 Hz, 2H, 6-H), 6.54, 5.85 (d, J = 2.4 Hz, 4H, 1-H, 3-H), 1.94 (s, 6H, 8-H), 1.25 (s, 18H , 16-H) ppm. meso: ¹ H-NMR (500 MHz ₁ C ₆ D ₆ ): δ = 7.79, 7.38 (d, J = 8.7 Hz ₁ 8H, 10-H, 11-H, 13-H, 14-H), 7.26 ( dd, J = 7.0 / 1.0 Hz, 2H, 5/7-H), 7.03 (dd, J = 8.4 / 1.0 Hz, 2H, 5 / 7- H) ₁ 6.96 (dd, J = 8.4 / 7.0 Hz, 2H , 6-H) ₁ 6.67, 5.84 (d, J = 2.4 Hz ₁ 4H, 1-H, 3-H) ₁ 1.86 (s, 6H, 8-H), 1.24 (s, 18H, 16-H) ppm ,

Comparative Example 4: Ethanediylbis [(2-methyl-4-phenyl) indenyl] zirconium dichloride 4

This bridged metallocene was chosen as a comparative substance for the polymerizations.

Comparative Example 5: Dimethylsilanediylbis [(2-methyl-4-phenyl) indenyl] zirconium dichloride 5

Example 6:

Representation of the supported catalysts I. Activation:

0.128 mmol of catalyst are dissolved in 20 ml of toluene in a heated flask under protective gas, and 6 ml (28.8 mmol, 1.672 g) of MAO (30% in toluene) are added. The mixture is stirred for one hour at room temperature.

2nd support:

In a heated flask under inert gas 6 g of SiO ₂ (Grace XPO 2107, dried) are introduced and with 30 ml of abs. Suspended toluene. The result is an easily stirrable suspension, to which then the activated catalyst (from 1.) is added. It is stirred for 10 min and then the solvent is removed in vacuo to a residual moisture of max. 5% away.

Examples 7-15: Homopolymerizations of ethylene

1.5 l of Exxsol are introduced into a 2 l steel autoclave and 15 mmol of an aluminum alkyl (for example triisobutylaluminum) are added. Subsequently, the reactor is brought to the desired temperature and built up an ethylene pressure of 7-15 bar. At the start of the polymerization, 9-18 μmol of the respective catalyst (see Table 1) are suspended in Exxsol. It is usually polymerized for one hour and the reaction is stopped by reducing the ethylene pressure. The polymer is filtered off and dried in vacuo at 8O ⁰ C. Finally, the yield and the molecular weight are determined.

14 4 8.7 μmol 10 bar 70 ° C 0.7 x 10 ⁶ g / mol

15 5 9 .0 μmol 10 bar 70 ° C 0.8 x 10 ⁶ g / mol

It thus turns out that only when using the unbridged metallocene catalysts according to the invention does the formation of ultrahigh molecular weight products occur.

Claims

claims

1. A process for the preparation of ultra-high molecular weight polymers of ethylene using at least one compound of formula I.

wherein:

M ^{1 represents} a transition metal of groups 3 to 6 of the Periodic Table of the Elements whose oxidation state is not equal to zero, and preferably Ti, Zr, Hf, V, Mo, Sc, Y, Cr and Nb, and

R ¹ , R ² , R ³ , R ⁴ , R ^{5 are} each the same or different and are hydrogen or a halogen atom or a C ¹ -C ₂₀ carbon-containing group, two or more of which can form a cyclic system with one another, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^{10 are} each the same or different and are hydrogen or a halogen atom or a Ci - C ₂ 0 carbon-containing group, of which two or more can form a cyclic system with each other, and X ^{1 is the} same Is hydrogen or a C ₁ -C 20 -carbon-containing group or

Is halogen, and X ² is hydrogen or a C ₁ -C 20 carbon-containing group or

Is halogen, and m is either 0, 1, 2 or 3, and n is either 0, 1, 2 or 3, and o is either 0, 1, 2 or 3, and p is either 0, 1, 2 or 3, and the sum of m, n, o and p is always equal to four.

2. The method according to claim 1, characterized in that at least one compound of the formula II

Formula Il

wherein:

M ^{1 represents} a transition metal of the 3rd to 6th group of the Periodic Table of the Elements, the oxidation state of which is not equal to zero, and preferably Ti, Zr, Hf, V,

Mo, Sc, Y, Cr and Nb, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ are the same or different and the same

Is hydrogen or a halogen atom or a C ₁ - C ₂ o- carbonaceous

Is hydrogen or a halogen atom or a C 1 -C 20 -carbon-containing compound

Group are two or more of which can form a cyclic system with each other, and X ¹ is hydrogen or a C ₁ -C 20 -carbon-containing group or

Is halogen, and X ² is hydrogen or a C ₁ -C ₂ 0 carbon-containing group or

Is halogen, and m is either 0, 1 or 2, and n is either 0, 1 or 2, and o is either 0, 1 or 2, and p is either 0, 1 or 2, and the sum of m, n , o and p is always equal to four, is used.

3. The method according to claim 1, characterized in that at least one compound of formula III

formula

wherein:

Is hydrogen or a halogen atom or a C 1 -C 20 -carbon-containing compound Group are two or more of which can form a cyclic system with each other, and X ¹ is hydrogen or a C ₁ - C 20 carbon-containing group or a

Is halogen, and X ² is hydrogen or a C ₁ -C 20 carbon-containing group or

Halogen atom is used.

4. The method according to claim 1, characterized in that at least one compound of formula IX

Formula IX

M ^{1 is} a transition metal of Group 4 of the Periodic Table of the Elements whose oxidation state is not equal to zero, and preferably Ti or Zr is, and

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²⁸ , R ²⁹ , R ³⁰ , R ^{31 are} each the same or different and equal hydrogen or a Haiogenatom or a C ₁ - C ₂ o- are carbon-containing group, two or more of which can form a cyclic system with one another, and X ¹ is hydrogen or a C ₁ -C 20 -carbon-containing group or

Is halogen, and X ² is hydrogen or a C ¹ -C 20 carbon-containing group or

Halogen atom is used.

5. The method according to claim 1, characterized in that the ethylene used contains further olefins selected from the group of 1-olefins with 2

20, preferably 2 to 10 C atoms, in particular propene, 1-butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene or 1-octene, styrene, dienes, preferably 1, 3 - Butadiene, 1, 4-hexadiene, Vinylnorbomen, norbornadiene, ethylnorbomadiene and cyclic olefins preferably norbornene, cyclopentadiene, tetracyclododecene or methylnorbornene and mixtures thereof.

6. The method according to claim 1, characterized in that the ethylene used with one or more 1-olefins having 2 to 8 carbon atoms, preferably propene, 1-butene, 1-pentene, 1-hexene, styrene, norbornene or butadiene, is copolymerized.

7. The method according to one or more of claims 1 to 6, characterized in that the compound of the formula I, II, III or IX used in the form of a catalyst system, preferably in supported form, is used.

8. The method according to claim 7, characterized in that the catalyst system contains at least one cocatalyst.

9. The method according to claim 8, characterized in that the catalyst system contains at least one Lewis acid as cocatalyst.

10. The method according to claim 1, characterized in that the available ethylene has a molecular weight of greater than 1 x 10 ⁶ mol / g.

11. A process for the preparation of a catalyst system according to claim 9, comprising the steps: a) preparation of a mixture of at least one compound of formula I, II, III or IX and at least one cocatalyst in a suitable solvent or suspending agent, b) applying the from C) removal of the majority of solvent from the resulting mixture d) isolation of the supported catalyst system e) optionally a prepolymerization of the resulting supported

Catalyst system with one or more olefinic monomer (s) to obtain a prepolymerized supported catalyst system.

12. Use of a catalyst system comprising at least one compound according to claim 1 to 4 and at least one cocatalyst for the production of ultra high molecular weight homo- or co-polymers based on ethylene.

13. Use according to claim 12, characterized in that the catalyst system is present in supported form.

14. Use of at least one compound according to claim 1 to 4 for the preparation of a catalyst system according to claim 12 or 13.