Process for the preparation of polyolefins
AssigneeTargor GmbH
InventorsAndreas Winter, Walter Spaleck, Bernd Bachmann
Life of this patent
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Abstract
Polyolefins with a molecular weight distribution M.sub.w /M.sub.n .gtoreq.3.0, which may be monomodal, bimodal or multimodal, can be obtained by polymerization or copolymerization of olefins with a catalyst system consisting of an aluminoxane and a transition metal component (metallocene), in which the transition metal component consists of at least one zirconocene of the formula I and at least one zirconocene of the formula Ia ##STR1## or alternatively of at least 2 zirconocenes of the formula I.
Claims13
A process for the preparation of a polyolefin having a molecular weight distribution M.sub.w /M.sub.n .gtoreq.3.0, which may be monomodal, bimodal or multimodal, by polymerization or copolymerization of an olefin of the formula R.sup.a CH.dbd.CHR.sup.b, in which R.sup.a and R.sup.b are identical or different and are a hydrogen atom or an alkyl radical with 1 to 14 carbon atoms, or R.sup.a and R.sup.b may from a ring system together with the atoms connecting them, at a temperature of 50-200.degree. C., at a pressure of 0.5 to 100 bar, in solution, in suspension or in a gas phase, in the presence of a catalyst which consists essentially of a transition metal component (metallocene) and an aluminoxane of the formula ##STR12## for the linear type and/or formula III ##STR13## for the cyclic type, in which the radicals R in the formulae II and III may be identical or different and are a C.sub.1 -C.sub.6 alkyl group, a C.sub.1 -C.sub.6 fluoroalkyl group, C.sub.6 -C.sub.18 aryl group, fluoroaryl group, or hydrogen and n is an integer from 0 to 50, or, of the aluminoxane, a mixture of an aluminoxane of the formula II and/or the formula III with an AlR.sub.3 compound, wherein at least two different zirconocenes with at least one zirconocene of the formula I and at least one zirconocene of the formula Ia are used as the transition component, ##STR14## in which
- R.sup.1 and R.sup.2 are identical or different and are a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, a C.sub.1 -C.sub.10 alkoxy group, a C.sub.6 -C.sub.10 aryl group, a C.sub.6 -C.sub.10 aryloxy group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkylaryl group, a C.sub.8 -C.sub.40 arylalkenyl group or a halogen atom,
- R.sup.3 is a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 alkyl group, which may be halogenated, a C.sub.6 -C.sub.10 aryl group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkyloxy group, a C.sub.8 -C.sub.40 arylalkenyl group, an --NR.sub.2.sup.10, --OR.sup.10, --SR.sup.10, --OSiR.sub.3.sup.10, --SiR.sub.3.sup.10 or --PR.sub.2.sup.10 radical, in which R.sup.10 is a halogen atom, a C.sub.1 -C.sub.10 alkyl group or a C.sub.6 -C.sub.10 aryl group,
- R.sup.4 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, a C.sub.7 -C.sub.40 alkylaryl group, an --NR.sub.2.sup.10, --OR.sup.10,
- --SR.sup.10, --OSiR.sub.3.sup.10, --SiR.sub.3.sup.10 or --PR.sub.2.sup.10 radical, in which R.sup.10 is a halogen atom, a C.sub.1 -C.sub.10 alkyl group or a C.sub.6 -C.sub.10 aryl group, where at least one R.sup.4 radicals per indenyl ring is different from hydrogen, or two or more R.sup.4 radicals form a ring system with the atoms connecting them,
- R.sup.5 and R.sup.6 are identical or different and are a halogen atom, a C.sub.1 -C.sub.10 alkyl group, which may be halogenated, a C.sub.6 -C.sub.10 aryl group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkyloxy group, a C.sub.8 -C.sub.40 arylalkenyl group, an --NR.sub.2.sup.10, --OR.sup.10, --SR.sup.10, --OSiR.sub.3.sup.10, --SiR.sub.3.sup.10 or --PR.sub.2.sup.10 radical, in which R.sup.10 is a halogen atom, a C.sub.1 -C.sub.10 alkyl group or a C.sub.6 -C.sub.10 aryl group,
- R.sup.7 is ##STR15## .dbd.BR.sup.11, .dbd.AlR.sup.11, --Ge--, --Sn--, --O--, --S--, .dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.11, .dbd.CO, .dbd.PR.sup.11 or .dbd.P(O)R.sup.11,
- where R.sup.11, R.sup.12 and R.sup.13 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, a C.sub.7 -C.sub.40 alkylaryl group, or R.sup.11 and R.sup.12 or R.sup.11 and R.sup.13 each form a ring with the atoms connecting them,
- M.sup.1 is silicon, germanium or tin,
- R.sup.8 and R.sup.9 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, a C.sub.7 -C.sub.40 alkylaryl group, or R.sup.8 and R.sup.9 each form a ring with the atoms connecting them,
- R.sup.14 and R.sup.15 are identical or different and are monocyclic or polycyclic hydrocarbon radical which may form a sandwich structure with the zirconium atom and
- m and n are identical or different and are zero, 1 or 2, with m plus n being equal to zero, 1 or 2.
A process for the preparation of a polyolefin having a molecularweight distribution M.sub.w /M.sub.n .gtoreq.3.0, which may be monomodal, bimodal or multimodal, by polymerization or copolymerization of an olefin of the formula R.sup.a CH.dbd.CHR.sup.b, in which R.sup.a and R.sup.b are identical or different and are a hydrogen atom or an alkyl radical with 1 to 14 carbon atoms, or R.sup.a and R.sup.b may from a ring system together with the atoms connecting them, at a temperature of 50-200 .degree. C., at a pressure of 0.5 to 100 bar, in solution, in suspension or in a gas phase, in the presence of a catalyst which consists essentially of a transition metal component (metallocene) and an aluminoxane of the formula ##STR16## for the linear type and/or formula III ##STR17## for the cyclic type, in which the radicals R in the formulae II and III may be identical or different and are a C.sub.1 -C.sub.6 alkyl group, a C.sub.1 -C.sub.6 fluoroalkyl group, C.sub.6 -C.sub.18, aryl group, fluororyl group, or hydrogen and n is an integer from 0 to 50, or, of the aluminoxane, a mixture of an aluminoxane of the formula II and/or the formula III with an AlR.sub.3 compound, wherein at least two different zirconocenes of the formula I are used as the transition component, ##STR18## in which
- R.sup.1 and R.sup.2 are identical or different and are a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, a C.sub.1 -C.sub.10 alkoxy group, a C.sub.6 -C.sub.10 aryl group, a C.sub.6 -C.sub.10 aryloxy group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkylaryl group, a C.sub.8 -C.sub.40 arylalkenyl group or a halogen atom,
- R.sup.3 is a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 alkyl group, which may be halogenated, a C.sub.6 -C.sub.10 aryl group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkyloxy group, a C.sub.8 -C.sub.40 arylalkenyl group, an --NR.sub.2.sup.10, --OR.sup.10, --SR.sup.10, --OSiR.sub.3.sup.10, --SiR.sub.3.sup.10 or --PR.sub.2.sup.10 radical, in which R.sup.10 is a halogen atom, a C.sub.1 -C.sub.10 alkyl group or a C.sub.6 -C.sub.10 aryl group,
- R.sup.4 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, a C.sub.7 -C.sub.40 alkylaryl group, an --NR.sub.2.sup.10, --OR.sup.10,
- --SR.sup.10, --OSiR.sub.3.sup.10, --SiR.sub.3.sup.10 or --PR.sub.2.sup.10 radical, in which R.sup.10 is a halogen atom, a C.sub.1 -C.sub.10 alkyl group or a C.sub.6 -C.sub.10 aryl group, where at least one R.sup.4 radicals per indenyl ring is different from hydrogen, or two or more R.sup.4 radicals form a ring system with the atoms connecting them,
- R.sup.5 and R.sup.6 are identical or different and are a halogen atom, a C.sub.1 -C.sub.10 alkyl group, which may be halogenated, a C.sub.6 -C.sub.10 aryl group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkyloxy group, a C.sub.8 -C.sub.40 arylalkenyl group, an --NR.sub.2.sup.10, --OR.sup.10, --SR.sup.10, --OSiR.sub.3.sup.10, --SiR.sub.3.sup.10 or --PR.sub.2.sup.10 radical, in which R.sup.10 is a halogen atom, a C.sub.1 -C.sub.10 alkyl group or a C.sub.6 -C.sub.10 aryl group,
- R.sup.7 is ##STR19## .dbd.BR.sup.11, .dbd.AlR.sup.11, --Ge--, --Sn--, --O--, --S--, .dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.11, .dbd.CO, .dbd.PR.sup.11 or .dbd.P(O)R.sup.11,
- where R.sup.11, R.sup.12 and R.sup.13 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, a C.sub.7 -C.sub.40 alkylaryl group, or R.sup.11 and R.sup.12 or R.sup.11 and R.sup.13 each form a ring with the atoms connecting them,
- M.sup.1 is silicon, germanium or tin,
- R.sup.8 and R.sup.9 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, a C.sub.7 -C.sub.40 alkylaryl group, or R.sup.8 and R.sup.9 each form a ring with the atoms connecting them,
- m and n are identical or different and are zero, 1 or 2, with m plus n being equal to zero, 1 or 2.
Dependencies are inferred from the claim text.