Process for the preparation of polyolefins having a broad molecular weight distribution

A process for the preparation of a monomodal, bimodal, or multimodal polyolefin having a molecular weight distribution M.sub.w /M.sub.n of .gtoreq.3.0, comprising:

• polymerizing 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 having 1 to 14 carbon atoms, or R.sup.a and R.sup.b, together with the atoms connecting them, form a ring, at a temperature for from -60.degree. to 200.degree. C., in suspension or in the gas phase, in the presence of a catalyst comprising a zirconocene component and an aluminoxane component, said aluminoxane component comprising an aluminoxane of the formula ##STR19## for the linear type or of the formula (III) ##STR20## for the cyclic type, where, in the formulae II and III, the radicals R are identical or different and are a C.sub.1 -C.sub.6 -alkyl group, a C.sub.1 -C.sub.6 -fluoroalkyl group, a C.sub.6 -C.sub.18 -aryl group, a C.sub.1 -C.sub.6 -fluoroaryl group or hydrogen, and n' is an number from 0 to 50, said aluminoxane component optionally containing a compound of the formula AlR.sub.3 ;
• said zirconocene component comprising at least one zirconocene of the formula I and at least one zirconocene of the formula Ia or alternatively at least 2 zirconocenes of the formula I ##STR21## 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.7 is ##STR22## .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,
• wherein
• 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.10 -alkyl group, a C.sub.1 -C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 -fluoroaryl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a C.sub.8 -C.sub.40 -arylalkenyl group or 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, together with the atoms connecting them, in each case form a ring, and
• M.sup.1 is silicon, germanium or tin,
• R.sup.8 and R.sup.9 are identical or different and are as defined for R.sup.11,
• R.sup.14 and R.sup.15 are identical or different and are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure together with the zirconium atom, and
• m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2, and
• A is ethylene, methylethylene, dimethyl silyl, diphenylsilyl, or phenyl(methyl) silyl.

A process for the preparation of a monomodal, bimodal, or multimodal polyolefin having a molecular weight distribution M.sub.w /M.sub.n of .gtoreq.3.0, comprising:

• polymerizing 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 having 1 to 14 carbon atoms, or R.sup.a and R.sup.b, together with the atoms connecting them, form a ring, at a temperature of from -60.degree. to 200.degree. C., in suspension or in the gas phase, in the presence of a catalyst comprising a zirconocene component and an aluminoxane component, said aluminoxane component comprising an aluminoxane of the formula ##STR23## for the linear type or of the formula (III) ##STR24## for the cyclic type, where, in the formulae II and III, the radicals R are identical or different and are a C.sub.1 -C.sub.6 -alkyl group, a C.sub.1 -C.sub.6 -fluoroalkyl group, a C.sub.6 -C.sub.18 -aryl group, a C.sub.1 -C.sub.6 -fluoroaryl group or hydrogen, and n' is a number from 0 to 50, said aluminoxane component optionally containing a compound of the formula AlR.sub.3 ;
• said zirconocene component comprising at least one zirconocene of the formula I ##STR25## 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 and R.sup.4 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, which is optionally halogenated, a C.sub.6 -C.sub.10 -aryl group, or a --NR.sub.2.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.5 and R.sup.6 are identical or different and are as defined for R.sup.3 and R.sup.4, with the proviso that R.sup.5 and R.sup.6 are not hydrogen,
• R.sup.7 is ##STR26## .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.10 -alkyl group, a C.sub.1 -C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 -fluoroaryl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a C.sub.8 -C.sub.40 -arylalkenyl group or 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, together with the atoms connecting them, in each case form ring, and
• M.sup.1 is silicon, germanium or tin,
• R.sup.8 and R.sup.9 are identical or different and are as defined for R.sup.11,
• R.sup.14 and R.sup.15 are identical or different and are a monocyclic or polycyclic hydrocarbon radicals which can form a sandwich structure together with the zirconium atom, and
• m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2,
• and at least one of the following zirconocenes:
• rac-phenyl(methyl)silyl(indenyl).sub.2 zirconium dichloride, diphenylmethylene(9-fluorenyl) (cyclopentadienyl)zirconium dichloride, isopropylidene(9-fluorenyl) (cyclopentadienyl)zirconium dichloride, rac-dimethylsilyl (2,3,5-trimethyl-1-cyclopentadienyl).sub.2 zirconium dichloride, rac-dimethylsilyl(indenyl).sub.2 zirconium dichloride, rac-dimethylgermyl(indenyl).sub.2 zirconium dichloride, rac-dimethylsilyl(indenyl).sub.2 dimethylzirconium, rac-phenyl(vinvl)silyl(indenyl).sub.2 zirconium dichloride, ##STR27## rac-dimethylsilyl (2,4-dimethylcyclopentadienyl).sub.2 zirconium dichloride, racisopropylidene(idenyl).sub.2 zirconium dichloride, racdimethylsilyl (2-methyl-4,5,6,7-tetrahydro-1-indenyl).sub.2 zirconium dichloride, rac-ethylene(indenyl).sub.2 zirconium dichloride, rac-methylene(3-t-butyl-1-cyclopentadienyl).sub.2 zirconium dichloride and rac-dimethylsilyl(4,7-dimethyl-1-idenyl).sub.2 zirconium dichloride,
• or alternatively at least two zirconocenes of the formula I.

A process for the preparation of a monomodal, bimodal, or multimodal polyolefin having a molecular weight distribution M.sub.w M.sub.n of .gtoreq.3.0, comprising:

• polymerizing 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 having 1 to 14 carbon atoms, or R.sup.a and R.sup.b, together with the atoms connecting them, form a ring, at a temperature of from -60.degree. to 200.degree. C., in suspension or in the gas phase, in the presence of a catalyst comprising a zirconocene component and an aluminoxane component, said aluminoxane component comprising an aluminoxane of the formula ##STR28## for the linear type or of the formula (III) ##STR29## for the cyclic type, where, in the formulae II and III, the radicals R are identical or different and are a C.sub.1 -C.sub.6 -alkyl group, a C.sub.1 -C.sub.6 -fluoroalkyl group, a C.sub.6 -C.sub.18 -aryl group, a C.sub.1 -C.sub.6 -fluoroaryl group or hydrogen, and N' is an integer from 0 to 50, said aluminoxane component optionally containing a compound of the formula AlR.sub.3 ;
• said zirconocene component comprising at least one zirconocene of the formula I and at least one zirconocene of the formula Ia or alternatively at least 2 zirconocenes of the formula I ##STR30## 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 and R.sup.4 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, which is optionally halogenated, a C.sub.6 -C.sub.10 -aryl group, or a --NR.sub.2.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.5 and R.sup.6 are identical or different and are as defined for R.sup.3 and R.sup.4, with the proviso that R.sup.5 and R.sup.6 are not hydrogen,
• R.sup.7 is ##STR31## .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.10 -alkyl group, a C.sub.1 -C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 -fluoroaryl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a C.sub.8 -C.sub.40 -arylalkenyl group or 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, together with the atoms connecting them, in each case form a ring, and
• M.sup.1 is silicon, germanium or tin,
• R.sup.8 and R.sup.9 are identical or different and are as defined for R.sup.11,
• R.sup.14 and R.sup.15 are identical or different and are monocyclic or polycyclic hydrocarbon radicals which can form a sandwich structure together with the zirconium atom, and
• m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2.