Hybrid catalyst composition for polymerization of olefins
The present invention relates to a new hybrid catalyst system for the polymerization of olefins and to a polymerization process carried out in the presence of said catalyst. The new hybrid catalyst system comprises a tridendate iron compound and a zirconocene having a bridge of at least three carbon atoms connecting two indenyl ligands.
1. A hybrid catalyst system for polymerization of olefins comprising a late transition metal component of formula (I),
wherein the variables have the following meaning:
R I4 independently of one another denote hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -C 20 -aryl, arylalkyl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, or SiR I8 3 , wherein the organic radicals R I4 can also be substituted by halogens,
R I13 -R I15 independently of one another denote hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, NR I9 2 , OR I9 , halogen, SiR I8 3 or five-, six- or seven-membered heterocyclyl, which comprises at least one atom from the group consisting of N, P, O or S, wherein the organic radicals R I13 -R I14 are unsubstituted or substituted by halogens, NR I9 2 , OR I9 or SiR I8 3 or two radicals R I13 -R I15 are bonded with one another to form a five-, six- or seven-membered ring or two radicals R I13 -R I15 are bonded with one another to form a five-, six- or seven-membered heterocyclyl, which comprises at least one atom from the group consisting of N, P, O or S, wherein at least one of the radicals R I12 -R I16 is selected from the group consisting of chlorine, bromine, iodine, CF 3 or OR I9 ,
R I12 are each, independently of one another, halogen, and
R I16 are each, independently of one another, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R I16 may also be substituted by halogen
R I1 -R I3 independently of one another denote hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, NR I9 2 , OR I9 , halogen, SiR I8 3 or five-, six- or seven-membered heterocycles, which comprise at least one atom from the group consisting of N, P, O or S, wherein the organic radicals R I1 -R I3 are optionally substituted by halogen radicals, C 1 -C 10 -alkyl radicals, C 2 -C 10 -alkenyl radicals, C 6 -C 20 -aryl radicals, NR I9 2 , OR I9 or SiR I8 3 and/or two radicals R I1 -R I3 are bonded with one another to form a five-, six- or seven-membered ring and/or two radicals R I1 -R I3 are bonded with one another to form a five-, six- or seven-membered heterocycle, which comprises at least one atom from the group consisting of N, P, O or S,
R I8 independently of one another denote hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
R I9 independently of one another denote hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, or SiR I8 3 , wherein the organic radicals R I9 is optionally substituted by halogen radicals, C 1 -C 10 -alkyl radicals, C 2 -C 10 -alkenyl radicals, or C 6 -C 20 -aryl radicals, and/or two radicals R I9 are bonded with one another to form a five- or six-membered ring,
X I independently of one another denote fluorine, chlorine, bromine, iodine, hydrogen, C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, NR I10 2 , OR I10 , SR I10 , SO 3 R I10 , OC(O)R I10 , CN, SCN, β-diketonate, CO, BF 4 − , PF 6 − or bulky non-coordinating anions, wherein the organic radicals X I is optionally substituted by halogen radicals, C 1 -C 10 -alkyl radicals, C 2 -C 10 -alkenyl radicals, or C 6 -C 20 -aryl radicals, and the radicals X I are optionally bonded with one another,
s is 1, 2, 3 or 4,
D I is a neutral donor,
t is 0 to 4
and
a metallocene component of formula (II)
wherein
R II1 to R II12 are the same or different from each other, hydrogen or a C 1 -C 40 radical, and optionally two adjacent R II1 to R II12 substituents form a ring comprising from 5 to 8 carbon atoms;
R II13 are the same or different and are each hydrogen atoms, C 1 -C 20 -alkyl-, C 3 -C 20 -cycloalkyl-, C 2 -C 20 -alkenyl-, C 6 -C 20 -aryl-, C 7 -C 20 -alkylaryl-, C 7 -C 20 -arylalkyl-, NR 3 2 —, PR 3 2 —, AsR 3 2 —, OR 3 —, SR 3 — or SeR 3 radicals, optionally containing silicon, germanium or halogen atoms;
X II are identical or different and are each a hydrogen atom, a halogen atom, or a C 1-22 radical, —OR II14 or NR II14 R II15 , the radicals R II14 and R II15 being each C 1 -C 32 radical, C 1 -C 32 fluoroalkyl or fluoroaryl radical, or two radicals X II are joined to one another; and
q is an integer from 3 to 8.
2. The catalyst system according to claim 1 wherein R I13 and R I16 are each, independently of one another, hydrogen, C 1 -C 22 -alkyl or halogen.
3. The catalyst system according to claim 1 wherein X II are same and each chlorine or a methyl radical.
4. The catalyst system according to claim 1 wherein the substituents R II1 to R I14 , R I16 , R I17 , R II10 , R II11 are each hydrogen radicals, q is 3, n is 2 and the substituents R II5 , R II8 , R II9 , R II12 each are methyl.
5. The catalyst system according to claim 1 further comprising a support.
6. A process for preparing polyethylene, wherein ethylene is polymerized in the presence of a catalyst system according to claim 1 .
7. The process according to claim 6 , wherein a monomer mixture of ethylene and/or C 3 -C 12 -1-alkenes which comprises at least 50 mol % of ethylene is used as monomers in the polymerization.