Metallocenes with ferrocenyl-substituted bridges used in...

Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing

Reexamination Certificate

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C556S011000, C556S012000, C556S043000, C556S053000, C556S143000, C556S144000, C526S114000, C526S115000, C526S117000, C526S348000, C526S351000, C526S352000, C526S943000

Reexamination Certificate

active

06239299

ABSTRACT:

The invention relates to new metallocenes and their use as catalysts in olefin polymerization.
Metallocenes of the metals of transition group IV of the Periodic Table of the Elements are highly active catalysts for the polymerization of olefins. The resulting polyolefins have new property combinations and supplement the product range of the polyolefins prepared hitherto using known conventional Ziegler-Natta catalysts.
It is known that catalysts based on unbridged, substituted and unsubstituted biscyclopentadienyl metallocenes in combination with aluminoxanes as cocatalyst can be used for the preparation of polyethylene and ethylene-&agr;-olefin copolymers (EP-B 128 046). It is also known that stereoregular polyolefins can be prepared using bridged, chiral metallocenes. For bridging the ligand systems, use is mostly made of dimethylsilanediyl groups (EP-A 485 823), methylphenylsilanediyl groups (EP-A 376 154), ethylene groups (Brintzinger et al., J. Organomet. Chem., 288 (1985) 63-67) and isopropylidene bridges (EP-A 351 391). Depending on the ligand type and the substituents, isotactic, syndiotactic, hemiisotactic, stereoblock-type and atactic homopolymers and copolymers having aliphatic or cyclic structures can be prepared. As ligands, preference is given to using substituted and unsubstituted cyclopentadienyl units (EP-A 316 155), substituted and unsubstituted indenyl units (Hoechst EP-A 485 823) and also substituted and unsubstituted cyclopentadienyl units in combination with unsubstituted fluorenyl groups (EP-A 351 391). Likewise, it is known that bridged metallocenes having a cyclopentadienyl system and a heteroatom ligand (constrained geometry catalyst) can also be used for the polymerization of olefins (U.S. Pat. No. 5,096,867).
Among these various types of metallocene, the bridged, chiral, substituted bisindenyl systems have attained particular importance. Thus, it was able to be shown that the type of substituents and the position of the substituents on the ligand of the metallocene have a significant influence on the reactivity of the catalyst system and the stereoregular structure of the polyolefins obtained. In addition, for targeted influencing of the polyolefin properties via the structure of the metallocenes, precise matching of the effects of ligands and bridge is desirable.
It is therefore an object of the invention to find further structural variants of bridged metallocenes as catalysts for the polymerization of olefins which give polyolefins, in particular polypropylenes, having relatively high molar masses and, at the same time, a narrow molar mass distribution.
It has now surprisingly been found that ferrocenyl-substituted, silanediyl-bridged metallocene systems are suitable catalysts for the preparation of polyolefins and in particular of polypropylenes having gradated properties.
The present invention accordingly provides metallocenes of the formula I
where M is a metal selected from the group consisting of Ti, Zr, Hf, V, Nb and Ta or an element selected from the group consisting of the lanthanides,
X
1
and X
2
are identical or different and are each a C
1
-C
10
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
10
-aryl group, a C
6
-C
10
-aryloxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
20
-arylalkyl group, a C
7
-C
20
-alkylaryl group, a C
8
-C
20
-arylalkenyl group, hydrogen or a halogen atom,
L
1
and L
2
a) are identical or different and are each an unsubstituted, monosubstituted or polysubstituted monocyclic or polycyclic hydrocarbon radical containing at least one cyclopentadienyl unit which can form a sandwich structure with M, or
b) L
1
is an unsubstituted, monosubstituted or polysubstituted monocyclic or polycyclic hydrocarbon radical containing at least one cyclopentadienyl unit which can form a sandwich structure with M, and L
2
is an amido, phosphido or arsenido radical of the formula
 where D is nitrogen, phosphorus or arsenic and E is as defined for X
1
and X
2
,
R is carbon, silicon, germanium or tin,
A and B are identical or different and are ferrocenyl-substituted radicals of the formula
 where R′ is a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, a C
2
-C
10
-alkenyl group, a C
7
-C
20
-arylalkyl group, a C
7
-C
20
-alkylaryl group, a C
8
-C
20
-arylalkenyl group, where B may also be as defined for X
1
or X
2
.
Preferred radicals A and B are ferrocenylalkyl radicals, particularly preferably ferrocenylethyl radicals.
Preferred ligands L
1
and/or L
2
are substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl radicals. Particular preference is given to cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4,5-benzindenyl, 2-methyl-4-arylindenyl and fluorenyl units and also ferrocene- and ruthenocene-substituted units as are described, for example, in EP-A-673 946.
According to the invention, the following metallocenes are particularly preferred:
bis(ferrocenylethyl)silanediyldicyclopentadienylzirconium dichloride,
bis(ferrocenylethyl)silanediyldiindenylzirconium dichloride,
bis(ferrocenylethyl)silanediylbis(2-methylindenyl)-zirconium dichloride,
bis(ferrocenylethyl)silanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride,
bis(ferrocenylethyl)silanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride,
bis(ferrocenylethyl)silanediylbis(2-methyl-4-naphthylindenyl)zirconium dichloride,
bis(ferrocenylethyl)silanediyldifluorenylzirconium dichloride,
bis(ferrocenylethyl)silanediyl(fluorenyl)(cyclopentadienyl)zirconium dichloride,
bis(ferrocenylethyl)silanediyl(fluorenyl)(indenyl)-zirconium dichloride,
bis(ferrocenylethyl)silanediyl(tetramethylcyclopentadienyl)(indenyl)zirconium dichloride,
methyl(ferrocenylethyl)silanediyldicyclopentadienylzirconium dichloride,
methyl(ferrocenylethyl)silanediyldiindenylzirconium dichloride,
methyl(ferrocenylethyl)silanediylbis(2-methylindenyl)zirconium dichloride,
methyl(ferrocenylethyl)silanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride,
methyl(ferrocenylethyl)silanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride,
methyl(ferrocenylethyl)silanediylbis(2-methyl-4-naphthylindenyl)zirconium dichloride,
methyl(ferrocenylethyl)silanediyldifluorenylzirconium dichloride,
methyl(ferrocenylethyl)silanediyl(fluorenyl)-(cyclopentadienyl)zirconium dichloride,
methyl(ferrocenylethyl)silanediyl(fluorenyl)(indenyl)-zirconium dichloride and
methyl(ferrocenylethyl)silanediyl(tetramethylcyclopentadienyl)(indenyl)zirconium dichloride.
The invention further provides a process for preparing the metallocenes I, which comprises reacting a compound of the formula II
where L
1
, L
2
, A, B and R are as defined for formula I and M′ is an alkali metal, preferably lithium, with a compound of the formula III
M(X′)
2
X
1
X
2
  (III),
 where M, X
1
and X
2
are as defined for formula I and X′ is a halogen atom, preferably chlorine. The metallocenes I can be prepared, for example, according to the following reaction scheme:
In the case of the unsymmetrical metallocenes, it is also possible to use various substituted or unsubstituted cyclopentadienyl, fluorenyl or amido, phosphido and arsenido radicals as ligands L
2
, where the substituents of these ligands are as defined for X
1
and X
2
or else are ferrocenyl- or ruthenocenyl-substituted or -fused.
The invention further provides for the use of the metallocenes of the invention as polymerization catalysts in the polymerization of olefins, and also provides an olefin polymerization process in which the metallocenes of the invention are used as catalysts.
In the olefin polymerization, preference is given to using a cocatalyst, for example an aluminoxane of the formula IV for the linear type:
and/or the formula V:
for the cyclic type, where, in the formulae IV and V, the radicals can be identical or different and are each a C
1
-C
6
-alkyl group and n is an integer of 1-50. Preferably, the radicals are identical and are methyl, isobutyl, phenyl or benzyl; particular preference is given to methyl. The aluminoxane can be prepared in various ways by known methods.

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