Bridged metallocene compounds, processes for the preparation...

Details Bridged metallocene compounds, processes for the preparation... Bridged metallocene compounds, processes for the preparation...

1996-05-30

2002-04-09

Wu, David W. (Department: 1713)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S013000, C556S043000, C556S053000, C556S058000, C502S117000, C502S152000, C526S127000, C526S160000, C526S943000

Reexamination Certificate

active

06369254

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to bridged metallocene compounds, to the corresponding ligands, to processes for preparing them and to the use of said metallocenes as components of catalysts for the polymerization of olefins.
2. Description of Related Art
Stereorigid chiral metallocene compounds possessing two bridged indenyl groups are known. They are used as components of catalysts for the polymerization of olefins, in particular for the preparation of stereo-regular polyolefins.
The numbering of the substituents on the indenyl group, to which reference is made in the present application, is as follows:
In metallocene compounds of the type indicated above, the indenyl groups are linked together by divalent radicals that have two or more carbon atoms, such as (CH
2
)
2
groups, or with atoms other than carbon, such as dimethylsilanediyl groups, which are generally joined to the indenyl rings in the 1 position. See, for example, European Patent Application EP-A-485 823.
European Patent Application EP-A-372 414 indicates two specific bis-indenyl metallocene compounds in which the divalent group linking the two indenyl ligands is joined in the 1 position to one indenyl ring and in the 2 position to the other indenyl ring (page 5, formulae II-1 and II-2).
International Patent Application WO 94/11406 describes a class of metallocene compounds comprising indenyl groups substituted in the 2 position. In particular, bis-indenyl compounds bridged in the 2 position on the indenyl rings are described.
SUMMARY OF THE INVENTION
New metallocene compounds have now been found which have two indenyl-type ligands linked together by a divalent group in the 4 position, and which can advantageously be used as catalyst components for the polymerization of olefins.
Therefore, in accordance with an aspect of the present invention, there are provided metallocene compounds of formula (I):
wherein
R
1
is a divalent group selected from CR
4
2
, C
2
R
4
4
, SiR
4
2
, Si
2
R
4
4
, Ger
4
2
, Ge
2
R
4
4
, R
4
2
SiCR
4
2
, NR
4
and PR
4
, in which the substituents R
4
, which may be identical or different, are atoms of hydrogen, C
1
-C
20
alkyl radicals, C
3
-C
20
cycloalkyl radicals, C
2
-C
20
alkenyl radicals, C
6
-C
20
aryl radicals, C
7
-C
20
alkaryl radicals or C
7
-C
20
aralkyl radicals and can contain atoms of Si or Ge, or, when R
1
is a CR
4
2
, C
2
R
4
2
, SiR
4
2
, Si
2
R
4
4
, GeR
4
2
, Ge
2
R
4
4
or R
4
2
SiCR
4
2
group, two or four substituents R
4
can form one or two rings that have from 2 to 6 carbon atoms;
R
2
and R
3
, which may be identical or different, are hydrogen atoms, C
1
-C
20
alkyl radicals, C
3
-C
20
cycloalkyl radicals, C
2
-C
20
alkenyl radicals, C
6
-C
20
aryl radicals, C
7
-C
20
alkaryl radicals or C
7
-C
20
aralkyl radicals and can contain atoms of Si or Ge, and in addition two substituents R
2
or R
3
adjacent on the same indenyl can form a ring containing from 4 to 8 carbon atoms;
M is an atom of a transition metal selected from those belonging to groups 3, 4, 5 or 6 or to the lanthanides or the actinides in the Periodic Table of the Elements (new IUPAC version);
the substituents X, which may be identical or different, are hydrogen atoms, halogen atoms, R, OR, SR, NR
2
or PR
2
groups, wherein the substituents R are C
1
-C
20
alkyl radicals, C
3
-C
20
cycloalkyl radicals, C
2
-C
20
alkenyl radicals, C
6
-C
20
aryl radicals, C
7
-C
20
alkaryl radicals or C
7
-C
20
aralkyl radicals and can contain atoms of Si or Ge.
According to another aspect of the present invention there is provided a compound of formula (II):
and its double bond isomers, wherein R
1
, R
2
and R
3
are defined as above.
According to a further aspect of the present invention there are provided methods for the preparation of the above described compounds of formula (II).
According to a still further aspect of the present invention there is provided a catalyst for the polymerization of olefins, comprising the product of the reaction between:
(A) a metallocene compound of formula (I) as described above, and
(B) an alumoxane, or one or more compounds capable of forming an alkyl metallocene cation.
According to a still further aspect of the present invention there is provided a process for the polymerization of olefins comprising the reaction of polymerization of one or more olefinic monomers in the presence of a catalyst as described above.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The metallocene compounds according to the invention can exist in the racemic or meso isomeric form.
The divalent group R
1
is preferably a C
2
R
4
4
group and, more preferably, it is a (CH
2
)
2
group.
The transition metal M is preferably selected from titanium, zirconium and hafnium, zirconium being particularly preferred.
The substituents X are preferably chlorine atoms or methyl radicals.
A particularly interesting class of metallocenes according to the invention is that of the compounds of formula (I) in which the group R
1
is a (CH
2
)
2
group, the substituents R
2
in the 5 and 6 positions and the substituents R
3
in the 3 positions are hydrogen atoms, the substituents R
2
in the 7 positions are different from hydrogen atoms, whereas the substituents R
3
in the 2 positions are preferably hydrogen atoms. Non-limiting examples of metallocene compounds belonging to the said class are:
rac- and meso-ethylenebis(7-methyl-4-indenyl)zirconium dichloride,
rac- and meso-ethylenebis(2,7-dimethyl-4-indenyl) zirconium dichloride.
Another particularly interesting class of metallocenes according to the invention is that of the compounds of formula (I) in which the group R
1
is a (CH
2
)
2
group, the substituents R
2
and the substituents R
3
in the 3 positions are hydrogen atoms, whereas the substituents R
3
in the 2 positions are different from hydrogen atoms. Non-limiting examples of metallocene compounds belonging to the said class are:
rac- and meso-ethylenebis(2-methyl-4-indenyl)zirconium dichloride.
A third particularly interesting class of metallocenes according to the invention is that of the compounds of formula (I) in which the group R
1
is a (CH
2
)
2
group, the substituents R
2
in the 5 and 7 positions and the substituents R
3
in the 3 positions are hydrogen atoms, whereas the substituents R
2
in the 6 positions are different from hydrogen atoms. Non-limiting examples of metallocene compounds belonging to the said class are:
rac- and meso-ethylenebis(6-methyl-4-indenyl)zirconium dichloride,
rac- and meso-ethylenebis(6-t-butyl-4-indenyl)zirconium dichloride,
rac- and meso-ethylenebis(2,6-dimethyl-4-indenyl) zirconium dichloride,
rac- and meso-ethylenebis(2-methyl-6-t-butyl-4-indenyl) zirconium dichloride.
A forth particularly interesting class of metallocenes according to the invention is that of the compounds of formula (I) in which the group R
1
is a (CH
2
)
2
group, the substituents R
2
in the 7 positions and the substituents R
3
in the 3 positions are hydrogen atoms, the substituents R
2
in the 5 and 6 positions form an alkylene ring, and the substituents R
3
in the 2 positions are different from hydrogen atoms. Non-limiting examples of metallocene compounds belonging to the said class are:
rac- and meso-ethylenebis(2-methyl-5,6-cyclotetramethylene-4-indenyl)zirconium dichloride.
A fifth particularly interesting class of metallocenes according to the invention is that of the compounds of formula (I) in which the group R
1
is a (CH
2
)
2
group, the substituents R
3
in the 3 positions are hydrogen atoms, and the substituents R
2
in the 6 and 7 positions form an alkylene ring. Non-limiting examples of metallocene compounds belonging to the said class are:
rac- and meso-ethylenebis(6,7-cyclotetramethylene-4-indenyl)zirconium dichloride,
rac- and meso-ethylenebis(2-methyl-6,7-cyclotetramethylene-4-indenyl)zirconium dichloride,
rac- and meso-ethylenebis(2,5-dimethyl-6,7-cyclotetramethylene-4-indenyl)zirconium dichloride.
A sixth particularly interesting class of metallocenes according to the invention is that of the compoun

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