Catalyst system for olefin polymerization

1. A catalyst system for olefin polymerization comprising:

an organic transition metal compound selected from the group consisting of transition metal complexes with at least one ligand of the formulae (IVa) to (IVe):

where the transition metal is selected from the group consisting of Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt and the elements of the rare earth metals,

E B , identical or different, is an element of group 15 of the Periodic Table of the Elements,

R 1B and R 4B are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical,

R 2B and R 3B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical, where R 2B and R 3B may optionally form a ring system optionally containing at least one heteroatom,

R 6B and R 8B are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical,

R 5B and R 9B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical,

where R 6B and R 5B or R 8B and R 9B may together form a ring system,

R 7B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical, where two radicals R 7A may optionally form a ring system,

R 10B and R 14B are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical,

R 11B , R 12B , R 12B′ and R 13B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical, where two or more geminal or vicinal radicals R 11B , R 12B , R 12B′ and R 13B may optionally form a ring system,

R 15B is hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical,

R 16B and R 17B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical,

R 19B is an organic radical which forms a 5- to 7-membered substituted or unsubstituted heterocyclic ring system,

n 1B is 0 or 1, with the compounds of the formula (IVc) being negatively charged when n 1B is 0, and

n 2B is an integer from 1 to 4,

heterocyclopentadienyl complexes of the formula (v):

[Z C —M C —X C n C ] m C   (V),

where

M C is chromium, molybdenum or tungsten, and

Z C has the formula (Va):

where:

E 1C -E 5C are each carbon or not more than one atom E 1C to E 5C is phosphorus or nitrogen,

A C is —NR 5C R 6C , —PR 5C R 6C , —OR 5C , —SR 5C or an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system,

R C is one of the following groups:

and, if A C is an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system, may also be

where

L 1C , L 2C are each silicon or carbon,

k C is 1 or when A 1C is an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system is 0,

X C is each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl, —NR 15C R 16C , OR 15C , —SR 15C , —SO 3 R 15C , —OC(O)R 15C , —CN, —SCN, β-diketonate, —CO, BF 4 − , PF 6 − or a bulky noncoordinating anion,

R 1C -R 16C are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR 17C 3 , where the organic radicals R 1C -R 16C may optionally be substituted by halogens and two geminal or vicinal radicals R 1C -R 16C may optionally be joined to form a five- or six-membered ring,

R 17C is each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl, and two geminal radicals R 17C may optionally be joined to form a five- or six-membered ring,

n C is 1, 2 or 3 and

m C is 1, 2 or 3,

imidochromium compounds of the formula (VI):

where:

R D is R 1D C═NR 2D , R 1D C═O, R 1D C═(OR 2D ), R 1D C═S, (R 1D ) 2 P═O, (OR 1D ) 2 P═O, SO 2 R 1D , R 1D R 2D C═N, NR 1D R 2D , BR 1D R 2D , C 1 -C 20 -alkyl, C 1 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, or C 7 -C 40 -alkylaryl,

X D is each, independently of one another, fluorine, chlorine, bromine, iodine, —NR 3D R 4D , —NP(R 3D ) 3 , —OR 3D , —OSi(R 3D ) 3 , —SO 3 R 3D , —OC(O)R 3D , β-diketonate, BF 4 − , PF 6 − or a bulky weakly coordinating or noncoordinating anion,

R 1D -R 4D are each, independently of one another, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl or hydrogen if bound to a carbon atom, where the organic radicals R 1D to R 4D may optionally bear inert substituents,

n D is 1 or 2,

m D is 1, 2 or 3,

L D is an uncharged donor and

y D is from 0 to 3,

[1,3,5-tri(methyl)-1,3,5-triazacyclohexane]chromium trichloride,

[1,3,5-tri(ethyl)-1,3,5-triazacyclohexane]chromium trichloride,

[1,3,5-tri(octyl)-1,3,5-triazacyclohexane]chromium trichloride,

[1,3,5-tri(dodecyl)-1,3,5-triazacyclohexane]chromium trichloride and

[1,3,5-tri(benzyl)-1,3,5-triazacyclohexane]chromium trichloride;

a cocatalyst comprising:

an ionic compound made up of anions of the formula (Ia),

[Al(OR 1 ) 4 ] −   (Ia)

where the radicals R 1 are each C(CF 3 ) 3 ;

Li + as a cation; and

an inorganic or organic support.

2. The catalyst system as claimed in claim 1 which further comprises an organometallic compound.

3. A process for preparing the catalyst system of claim 2 comprising:

firstly bringing the support into contact with the organometallic compound, thereby forming a reaction product and adding the organic transition metal compound and the cocatalyst to the reaction product.

4. A catalyst system for the polymerization of olefins comprising:

an organic transition metal compound selected from the group consisting of transition metal complexes with at least one ligand of the formulae (IVa) to (IVe):

where the transition metal is selected from the group consisting of Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt and the elements of the rare earth metals,

E B , identical or different, is an element of group 15 of the Periodic Table of the Elements,

R 1B and R 4B are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical

R 2B and R 3B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical, where R 2B and R 3B may optionally form a ring system optionally containing at least one heteroatom,

R 6B and R 8B are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical,

R 5B and R 9B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical,

where R 6B and R 5B or R 8B and R 9B may together form a ring system,

R 7B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical, where two radicals R 7A may optionally form a ring system,

R 10B and R 14B are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical,

R 11B , R 12B , R 12B′ and R 13B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical, where two or more geminal or vicinal radicals R 11B , R 12B , R 12B′ and R 13B may optionally form a ring system,

R 15B hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical,

R 16B and R 17B are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted hydrocarbon radical,

R 19B is an organic radical which forms a 5- to 7-membered substituted or unsubstituted heterocyclic ring system,

n 1B is 0 or 1, with the compounds of the formula (IVc) being negatively charged when n 1B is 0, and

n 2B is an integer from 1 to 4,

heterocyclopentadienyl complexes of the formula (V):

[Z C —M C —X C n C   (V),

where

M C is chromium, molybdenum or tungsten, and

Z C has the formula (Va):

where:

E 1C -E 5C are each carbon or not more than one atom E 1C to E 5C is phosphorus or nitrogen,

A C is —NR 5C R 6C , —PR 5C R 6C , —OR 5C , —SR 5C or an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system,

R C is one of the following groups:

and, if A C is an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaromatic ring system, may also be

where

L 1C , L 2C are each silicon or carbon,

k C is 1 or when A 1C is an unsubstituted, substituted or fused, partially unsaturated heterocyclic or heteroaroratic ring system is 0,

X C is each, independently of one another, fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl, NR 15C R 16C , —OR 15C , —SR 15C , —SO 3 R 15C , —OC(O)R 15C , —CN, —SCN, β-diketonate, —CO, BF 4 − , PF 6 − or a bulky noncoordinating anion,

R 1C -R 16C are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, SiR 17C 3 , where the organic radicals R 1C -R 16C may optionally be substituted by halogens and two geminal or vicinal radicals R 1C -R 16C may optionally be joined to form a five- or six-membered ring,

R 17C is each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl, and two geminal radicals R 17C may optionally be joined to form a five- or six-membered ring,

n C is 1, 2 or 3 and

m C is 1, 2 or 3,

imidochromium compounds of the formula (VI):

where:

R D is R 1D C═NR 2D , R 1D C═O, R 1D C═(OR 2D ), R 1D C═S, (R 1D ) 2 P═O, (OR 1D ) 2 P═O, SO 2 R 1D , R 1D R 2D C═N, NR 1D R 2D , BR 1D R 2D , C 1 -C 20 -alkyl, C 1 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, or C 7 -C 40 -alkylaryl,

X D is each, independently of one another, fluorine, chlorine, bromine, iodine, —NR 3D R 4D , —NP(R 3D ) 3 , —OR 3D , —OSi(R 3D ) 3 , SO 3 R 3D , —OC(O)R 3D , β-diketonate, BF 4 − , PF 6 − or a bulky weakly coordinating or noncoordinating anion,

R 1D -R 4D are each, independently of one another, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, C 7 -C 40 -alkylaryl or hydrogen if bound to a carbon atom, where the organic radicals R 1D to R 4D may optionally bear inert substituents,

n D is 1 or 2,

m D is 1 or 2,

L D is an uncharged donor and

y D is from 0 to 3,

[1,3,5-tri(methyl)-1,3,5-triazacyclohexane]chromium trichloride,

[1,3,5-tri(ethyl)-1,3,5-triazacyclohexane]chromium trichloride,

[1,3,5-tri(octyl)-1,3,5-triazacyclohexane]chromium trichloride,

[1,3,5-tri(dodecyl)-1,3,5-triazacyclohexane]chromium trichloride and

[1,3,5-tri(benzyl)-1,3,5-triazacyclohexane]chromium trichloride;

an organometallic compound; a cocatalyst comprising an ionic compound made up of anions of the formula (Ia):

[Al(OR 1 ) 4 ] −   (Ia)

where the radicals R 1 are each C(CF 3 ) 3 ;

L + as a cation; and

an inorganic or organic support

which is obtained by a process comprising firstly bringing the support into contact with an organometallic compound, thereby forming a reaction product and adding the organic transition metal compound and the cocatalyst to the reaction product.

5. A process comprising polymerizing olefins with the catalyst system of claim 1 .