Stereorigid metallocene compounds

Details Stereorigid metallocene compounds Stereorigid metallocene compounds

1999-11-02

2002-06-25

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S159000, C526S160000, C526S348200, C526S348500, C526S348600, C520S001000, C520S001000, C520S001000

Reexamination Certificate

active

06410661

ABSTRACT:

The present invention relates to special stereorigid metallocene compounds and a process for the preparation of polyolefins in the presence of these special stereorigid metallocene compounds.
The literature discloses the preparation of polyolefins using soluble metallocene compounds in combination with aluminoxanes or other cocatalysts which, owing to their Lewis acidity, can convert the neutral metallocene into a cation and stabilize it (EP 129 368, EP 351 392).
The conference volume of the 1st Journal of organometallic Chemistry Conference on Applied Organometallic Chemistry, page 136, describes metallocenes which have a substituted tricyclic hydrocarbon as a ligand system.
The use of soluble metallocene compounds based on bis(cyclopentadienyl)zirconiumdialkyl or bis(cyclopentadienyl)zirconium dihalide in combination with oligomeric aluminoxanes gives atactic polymers which, owing to their unbalanced and inadequate product properties, are only of little importance industrially. Moreover, certain olefin copolymers are not obtainable.
Derivatives of zirconocene dichloride in which the two substituted cyclopentadienyl groups are linked to one another via a methylene, ethylene or dimethylsilylene bridge can, owing to their conformational rigidity, be used as catalysts for the isospecific polymerization of olefins (Chem. Lett. (1989), 1853 to 1856 or EP A 0 316 155). Metallocenes having (substituted) indenyl radicals as ligands are of particular importance for the preparation of highly isotactic polymers having high crystallinity and a high melting point (EP 485 823, EP 530 647).
Also of major interest are polyolefins whose property profile is between these two extremes.
It is an object of the present invention to provide a metallocene compound which avoids the disadvantages of the prior art and is suitable for the preparation of polyolefins.
We have found that this object is achieved by a stereorigid metallocene compound of the formula I
where
M is a metal of Group IIlb, IVb, Vb or VIb of the Periodic Table of the Elements,
R
1
and R
2
are identical or different and are each hydrogen, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
10
-alkyl, C
1
-C
10
-alkoxy, C
6
-C
10
-aryl, C
6
-C
25
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl or C
7
-C
40
-arylalkenyl, OH, halogen or NR
15
21
where R
15
is halogen, C
1
-C
10
-alkyl or C
6
-C
10
-aryl, or R
1
and R
2
, together with the atoms linking them, form a ring system,
R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are identical or different and are each hydrogen, a C
1
-C
40
-hydrocarbon-containing-group, such as C
1
-C
10
-alkyl, which may be halogenated, C
6
-C
30
-aryl, which may be halogenated, C
6
-C
20
-aryloxy, C
2
-C
12
-alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl or C
8
-C
40
-arylalkenyl, halogen, SiR
17
3
, NR
17
2
, SiOR
17
3
, SiSR
17
3
or PR
17
2
, where R
17
are identical or different and are each halogen, C
1
-C
10
-alkyl or C
6
-C
10
-aryl or form a ring system, or two or more neighboring radicals R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11 , R
14
, R
15
and R
16
, together with the atoms linking them, form a ring system which preferably contains 4 to 40, particularly preferably 6 to 20, carbon atoms,
and R
12
and R
13
are identical or different and are each hydrogen, a C
6
-C
30
-aryl-containing group, such as C
6
-C
30
-aryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl or C
8
-C
40
-arylalkenyl, each of which may be halogenated, and at least one of the radicals R
12
and R
13
is not hydrogen.
In compounds of the formula I
M is preferably a metal of Group IVb of the Periodic Table of the Elements, such as titanium, zirconium or hafnium, in particular zirconium,
R
1
and R
2
are identical and are each C
1
-C
4
-alkyl or halogen, such as fluorine, chlorine, bromine or iodine, in particular chlorine,
R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are identical or different and are each hydrogen, C
1
-C
10
-alkyl or C
6
-C
24
-aryl, or two or more neighboring radicals R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
14
, R
15
and R
16
, together with the atoms linking them, form an aromatic or aliphatic ring system of 4 to 20 carbon atoms,
and R
12
and R
13
are identical or different and are each hydrogen or C
6
-C
24
-aryl and at least one of the radicals R
12
and R
13
is not hydrogen.
Compounds of the formula I where
M is zirconium,
R
1
and R
2
are identical and are each halogen, in particular chlorine,
R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, R
14
, R
15
and R
16
are identical or different and are each hydrogen, C
1
-C
4
-alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl or isobutyl, or C
6
-C
14
-aryl, such as phenyl or naphthyl, or R
11
and R
15
form a ring system, and R
12
is hydrogen and R
13
is C
6
-C
14
-aryl, are particularly preferred.
Examples of novel metallocene compounds are:
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-phenyl-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-phenyl-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]-dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-phenyl-h
5
-tetrahydropentalene]dichlorotitanium
[Isopropylidene-(2-phenyl-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]-dichlorotitanium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-phenyl-h
5
-tetrahydropentalene]dichlorohafnium
[Isopropylidene-(2-phenyl-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]-dichlorohafnium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-phenyl-h
5
-tetrahydropentalene]bisdimethylaminozirconium
[Isopropylidene-(2-phenyl-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]bisdimethylaminozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(p-tolyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(p-tolyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]-dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(m-tolyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(m-tolyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]-dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(o-tolyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(o-tolyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]-dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(2,3-dimethylphenyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(2,3-dimethylphenyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(2,4-dimethylphenyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(2,4-dimethylphenyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(2,6-dimethylphenyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(2,6-dimethylphenyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(3,5-dimethylphenyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(3,5-dimethylphenyl)-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-tetramethylphenyl-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-tetramethylphenyl-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-tetramethylphenyl-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-tetramethylphenyl-&eegr;
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(2,4-dimethoxyphenyl)-h
5
-tetrahydropentalene]dichlorozirconium [Isopropylidene-(2-(2,4-dimethoxyphenyl)-n
5
-cyclopentadienyl)-(9-fluorenyl)]dichlorozirconium
[4-(h
5
-Fluorenyl)-4,6,6-trimethyl-2-(3,5-dimethoxyphenyl)-h
5
-tetrahydropentalene]dichlorozirconium
[Isopropylidene-(2-(3,5-dimethoxyphenyl)-&eegr;
5
-cyclopentadienyl)-(9-fluoreny

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