Catalyst system composed of metallocenes comprising...

Details Catalyst system composed of metallocenes comprising... Catalyst system composed of metallocenes comprising...

2000-10-11

2003-03-25

Mulcahy, Peter D. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S104000, C502S117000, C526S129000, C526S160000, C526S943000, C556S053000

Reexamination Certificate

active

06537943

ABSTRACT:

The present invention relates to a catalyst system comprising metallocenes having fluorine-containing substituents, a process for preparing it and its use for the polymerization of olefins.
One of the first reactions in which a metallocene of transition group IV containing fluorine-containing ligands is reacted is the flash pyrolysis of Cp
2
Ti(C
6
F
5
)
2
(J. Organomet. Chem. 1963, 1, 98; J. Organomet. Chem. 1964, 2, 206). Here, migration of a fluorine atom occurs.
Perfluorinated ligands play an important role in the stabilization of electron-deficient metal centers. For example, cationic metallocenes are stabilized in the Ziegler-Natta polymerization by perfluorinated tetraphenylborates (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41, 1220).
An electron-deficient metal center can also be stabilized by means of a partially fluorinated anion in the reaction of dimethylzirconocene compounds with [PhMe
2
NH]
+
[B(C
6
H
4
F)
4
]
−
(Organometallics 1991, 10, 3910). The coordination of an F atom of the anion to the metal center can be confirmed by means of
19
F-NMR spectroscopy.
The reaction of butadiene(zirconocene) with the Lewis acid B(C
6
F
5
)
3
gives a betaine in which the cationic metal center is stabilized by coordination of a fluorine atom of the pentafluorophenyl radical (Angew. Chem. 1995, 107, 1867). In this case, the coordination is only weak, so that the labile ligand can be displaced by monomers.
The compounds mentioned up to now describe interactions of cationic metallocenes with aromatic fluorine-containing ligands. The use of partially fluorinated or perfluorinated aliphatic substituents on cyclopentadienyl ligands of the metallocenes has only been described in isolated cases.
Thus, a titanocene in which a trifluoromethyl group is bound to a cyclopentadienyl ligand is known (JACS 1986, 108, 4228).
Intramolecular coordination of a fluorine atom to the metal center is hardly possible here because of the geometry.
It is an object of the present invention to provide a catalyst system comprising metallocenes having fluorine-containing substituents.
We have found that this object is achieved by a catalyst system which comprises at least one metallocene having fluorine-containing substituents and at least one cocatalyst component and may be supported, and by a process for preparing it and its use in the polymerization of propylene.
The catalyst system of the present invention comprises
(a) at least one cocatalyst,
(b) at least one organometallic compound of the formula (I)
where
M
1
is a metal of group 3, 4, 5 or 6 of the Periodic Table of the Elements or a lanthanide or actinide,
R
1
are identical or different and are each a hydrogen atom, a C
1
-C
30
group such as C
1
-C
25
-alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C
2
-C
25
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
24
-aryl, C
5
-C
24
-heteroaryl such as pyridyl, furyl or quinolyl, C
7
-C
30
-arylalkyl, C
7
-C
30
-alkylaryl, C
1
-C
12
-alkoxy, SiR
3
, where R
3
are identical or different and are each a hydrogen atom or a C
1
-C
40
group such as C
1
-C
20
-alkyl, C
1
-C
10
-fluoroalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl or C
8
-C
40
-arylalkenyl, or two or more radicals R
1
may be joined to one another in such a way that the radicals R
1
and the atoms of the cyclopentadienyl ring which connect them form a C
4
-C
24
ring system which may in turn be substituted,
R
2
are identical or different and are each fluorine-containing C
1
-C
25
-alkyl, fluorine-containing C
1
-C
25
-alkenyl, fluorine-containing C
6
-C
24
-aryl, fluorine-containing C
7
-C
30
-arylalkyl or fluorine-containing C
7
-C
30
-alkylaryl,
r, n are identical or different and are 1, 2, 3, 4 or 5,
m, q are identical or different and are 0, 1, 2, 3 or 4,
q+r is 5 when v=0, and q+r is 4 when v=1,
m+n is 5 when v=0, and m+n is 4 when v=1,
s, t are identical or different and are each an integer from 1 to 20,
L are identical or different and are each a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms, e.g. C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
1
-C
20
-alkoxy, C
6
-C
14
-aryloxy or C
6
-C
40
-aryl,
x is an integer from 1 to 4, with x preferably being 2 when M
1
=Ti, Zr or Hf,
Z is a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1,
and, if desired,
(c) at least one support.
Z is particularly preferably an M
2
R
4
R
5
group, where M
2
is carbon, silicon, germanium or tin and R
4
and R
5
are identical or different and are each a C
1
-C
20
-hydrocarbon group such as C
1
-C
10
-alkyl or C
6
-C
14
-aryl.
Z is preferably CH
2
, CH
2
CH
2
, CH(CH
3
)CH
2
, CH(C
4
H
9
)C(CH
3
)
2
, C(CH
3
)
2
, (CH
3
)
2
Si, (CH
3
CH
2
)
2
Si, (CH
3
)((CH
3
)
3
C)Si, (CH
3
)
2
Ge, (CH
3
)
2
Sn, (C
6
H
5
)
2
Si, (C
6
H
5
)(CH
3
)Si, (C
6
H
5
)
2
Ge, (C
6
H
5
)
2
Sn, (CH
2
)
4
Si, CH
2
Si(CH
3
)
2
, o-C
6
H
4
or 2,2′-(C
6
H
4
)
2
. It is also possible for Z together with one or more radicals R
1
and/or R
2
to form a monocyclic or polycyclic ring system.
Preference is given to chiral bridged metallocenes of the formula 1, in particular ones in which v is 1 and one or both cyclopentadienyl rings are substituted in such a way that they form an indenyl ring. The indenyl ring is preferably substituted, in particular in the 2 position, 4 position, 2,4,5 positions, 2,4,6 positions, 2,4,7 positions or 2,4,5,6 positions, by C
1
-C
20
groups such as C
1
-C
10
-alkyl or C
6
-C
20
-aryl, where two or more substituents of the indenyl ring can also together form a ring system.
In formula (I), it is particularly preferred that
M
1
is a metal of group 4 of the Periodic Table of the Elements, e.g. Ti, Zr or Hf,
R
1
are identical or different and are each a hydrogen atom, a C
1
-C
30
group such as C
1
-C
25
-alkyl, in particular methyl, ethyl, tert-butyl, cyclohexyl or octyl, C
2
-C
25
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
24
-aryl, C
5
-C
24
-heteroaryl such as pyridyl, furyl or quinolyl, C
7
-C
30
-arylalkyl, C
7
-C
30
-alkylaryl or C
1
-C
12
-alkoxy, SiR
3
, where R
3
are identical or different and are each a hydrogen atom or a C
1
-C
40
group such as C
1
-C
20
-alkyl, C
1
-C
10
-fluoroalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl or C
8
-C
40
-arylalkenyl, or two or more radicals R
1
may be joined to one another in such a way that the radicals R
1
and the atoms of the cyclopentadienyl ring which connect them form a C
4
-C
24
ring system which may in turn be substituted,
R
2
are identical or different and are each fluorine-containing C
1
-C
25
-alkyl, fluorine-containing C
1
-C
25
-alkenyl, fluorine-containing C
6
-C
24
-aryl, fluorine-containing C
7
-C
30
-arylalkyl or fluorine-containing C
7
-C
30
-alkylaryl,
r, n are identical or different and are 1, 2, 3, 4 or 5,
m, q are identical or different and are 0, 1, 2, 3 or 4,
q+r is 5 when v=0, and q+r is 4 when v=1,
m+n is 5 when v=0, and m+n is 4 when v=1,
s, t are identical or different and are each an integer from 1 to 20,
L are identical or different and are each a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms, in particular C
1
-C
20
-alkyl, C
2
-C
20
-alkenyl, C
1
-C
20
-alkoxy, C
6
-C
14
-aryloxy or C
6
-C
40
-aryl,
x is an integer from 1 to 4, with x preferably being 2 when M
1
=Ti, Zr or Hf
Z is a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1.
Illustrative but nonlimiting examples of organometallic compounds used according to the present invention are:
bis(&eegr;
5
-2′, 2′, 2′-trifluoroethyl)cyclopentadienyl)titanium dichloride
bis(&eegr;
5
-1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienyl)titanium dichloride
bis(&eegr;
5
-1′H, 1′H, 2′H, 2′H-perfluoroh

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