Process for preparing a metallocene catalyst system

Details Process for preparing a metallocene catalyst system Process for preparing a metallocene catalyst system

1998-01-29

2001-01-23

Bell, Mark L. (Department: 1755)

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

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

C502S104000, C502S121000, C502S124000, C502S128000, C502S129000, C502S132000, C502S134000

Reexamination Certificate

active

06177376

ABSTRACT:

The present invention relates to a process for preparing a metallocene catalyst system which is suitable for the polymerization of olefins. The intermediates formed in the process are not isolated, but are used directly in solution for further process steps.
Hydrocarbon-substituted metallocene compounds such as monoalkyl- and dialkyl- or monoaryl- and diaryl-metallocene compounds form, in combination with specific cocatalysts, active catalyst systems which are suitable for the polymerization of olefins (EP 468537, EP 427697,
J. Am. Chem. Soc.
1989, 111, 2728). In addition, application of such systems to a support allows an improved polymer morphology to be achieved (EP 614468, EP 507876).
Processes known hitherto from the literature for preparing hydrocarbon-substituted metallocene catalyst systems have the disadvantage that the metallocenes first have to be isolated, as a result of which yield losses cannot be avoided. Activation of the metallocene and application of the metallocene to a support represent additional process steps.
It is therefore an object of the present invention to provide a process in which a polymerization-active hydrocarbon-substituted metallocene catalyst is prepared in a simple and economical manner.
This object is achieved by a process for preparing a metallocene catalyst system in which a metallocene starting compound is reacted in a solvent with a compound capable of transferring hydrocarbon radicals and the resulting metallocene compound which is a-substituted by one or more hydrocarbon radicals is converted in solution without isolation into a polymerization-active catalyst system by means of an activator. The catalyst system obtained in solution can be used for a polymerization process without prior isolation.
For the purposes of the present invention, the term solution or solvent also encompasses suspensions or suspension media, i.e. the starting materials used in the process of the invention and also the products obtained can be partly or completely dissolved or can be partly or completely in suspended form.
Metallocene starting compounds employed can be, for example, cyclopentadienyl complexes. These can be, for example, bridged or unbridged biscyclopentadienyl complexes as described, for example, in EP 129 368, EP 561 479, EP 545 304 or EP 576 970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes which are described, for example, in EP 416 815, multinuclear cyclopentadienyl complexes as described in EP 632 063, T7-ligand-substituted tetrahydropentalenes as described in EP 659 758 or n-ligand-substituted tetrahydroindenes as described in EP 661 300.
Preferred metallocene starting compounds are unbridged or bridged metallocene compounds of the formula I,
where
M
1
is a metal of transition group 3, 4, 5 or 6 of the Periodic Table of the Elements, in particular Ti, Zr or Hf,
R
1
are identical or different and are each a hydrogen atom or SiR
3
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 R
1
is 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, fluorine-containing C
1
-C
25
-alkyl, fluorine-containing C
6
-C
24
-aryl, fluorine-containing C
7
-C
30
-arylalkyl, fluorine-containing C
7
-C
30
-alkylaryl or C
1
-C
12
-alkoxy, or two or more radicals R
1
can be connected 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 in turn may be substituted,
R
2
are identical or different and are each a hydrogen atom or SiR
3
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
14
-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 R
2
is 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, e.g. pyridyl, furyl or quinolyl, C
7
-C
30
-arylalkyl, C
7
-C
30
-alkylaryl, fluorine-containing C
1
-C
25
-alkyl, fluorine-containing C
6
-C
24
-aryl, fluorine-containing C
7
-C
30
-arylalkyl, fluorine-containing C
7
-C
30
-alkylaryl or C
1
-C
12
-alkoxy, or two or more radicals R
2
can be connected to one another in such a way that the radicals R
2
and the atoms of the cyclopentadienyl ring which connect them form a C
4
-C
24
-ring system which in turn may be substituted,
l is 5 when v=0, and l is4 when v=1,
m is 5when v=0,and m is 4 when v=1,
X
1
can be identical or different and are each a hydrogen atom, a halogen atom or OR
6
, SR
6
, OSiR
3
6
, SiR
3
6
, PR
2
6
or NR
2
6
, where R
6
is a halogen atom, a C
1
-C
10
alkyl group, a halogenated C
1
-C
10
alkyl group, a C
6
-C
20
- aryl group or a halogenated C
6
-C
20
-aryl group, or
X
1
is a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group, preferably a halogen atom,
o is an integer from 1 to 4, preferably 2,
Z is a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
Examples of Z are groups M
2
R
4
R
5
, 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-containing group such as C
1
-C
10
-alkyl, C
6
-C
14
-aryl or trimethylsilyl. 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
)
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 metallocene starting compounds of the formula I, in particular those 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; 4; 2,4,5; 2,4,6; 2,4,7 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. Chiral bridged metallocene starting compounds of the formula I can be used as racemic or pure meso compounds. However, it is also possible to use mixtures of a racemic compound and a meso compound.
Examples of metallocene starting compounds are:
dimethylsilanediylbis(indenyl)zirconium dichloride
dimethylsilanediylbis(4-naphthylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methylbenzindenyl)zirconium dichloride
dimethylsilanediylbis(2-methylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-(1-naphthyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-(2-naphthyl)indenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-phenylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-t-butylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-isopropylindenyl)zirconium dichloride
dimethylsilanediylbis(2-methyl4-ethylindenyl)zirconium dichloride
dimethylsilyl-bis-(indenyl)hafnium dichloride
dimethylsilanediylbis(2-methyl4-&agr;-acenaphthindenyl)zirconium dichloride
dimethylsilanediylbis(2,4-dimethylindenyl)zirconium dichioride
dimethylsilanediylbis(2-ethylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-ethylindenyl)zirconium dichloride
dimethylsilanediylbis(2-ethyl4-phenylindenyl)zirconium dic

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