2-substituted disindenylmetallocenes, process for their...

Details 2-substituted disindenylmetallocenes, process for their... 2-substituted disindenylmetallocenes, process for their...

1999-07-13

2001-09-18

Wood, Elizabeth D. (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...

C502S103000, C526S160000, C556S007000, C556S008000, C556S011000, C556S014000, C556S019000, C556S020000, C556S021000, C556S022000, C556S043000, C556S053000, C556S058000

Reissue Patent

active

RE037384

ABSTRACT:

The present invention relates to novel 2-substituted bisindenylmetallocenes which can very advantageously be used as catalysts in the preparation of polyolefins of high molecular weight.
Polyolefins of high molecular weight are particularly important for the production of films, sheets or large hollow elements, such as, for example, tubes or moldings.
Chiral metallocenes are, in combination with aluminoxanes, active, stereospecific catalysts for the preparation of polyolefins (U.S. Pat. No. 4,769,510). These metallocenes also include substituted indene compounds. Thus, for example, the use of the ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride/aluminoxane catalyst system is known for the preparation of isotactic polypropylene (cf. EP-A 185 918). Both this and numerous other polymerization processes coming under the prior art have, in particular, the disadvantage that, at industrially interesting polymerization temperatures, only polymers having an unacceptably low molecular weight are obtained.
Surprisingly, it has now been found that novel 2-substituted bisindenylmetallocenes are suitable catalysts for the preparation of olefin polymers of high isotacticity, narrow molecular weight distribution and high molecular weight.
The present invention therefore provides the compounds of the formula I below
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R
1
and R
2
are identical or different and are a hydrogen atom, 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
40
-arylalkyl group, a C
7
-C
40
-alkyl-aryl group, a C
8
-C
40
-arylalkenyl group or a halogen atom,
R
3
and R
4
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, which may be halogenated, a C
6
-C
10
-aryl group, an —NR
2
10
, —SR
10
, —OSiR
3
10
, —SiR
3
10
or —PR
2
10
radical in which R
10
is a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group,
R
5
and R
6
are identical or different and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
are not hydrogen,
═BR
11
, ═AlR
11
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
11
, ═CO, ═PR
11
or ═P(O)R
11
, where
R
11
, R
12
and R
13
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-fluoroalkyl group, a C
6
-C
10
-aryl group, a C
6
-C
10
-fluoroaryl group, a C
1
-C
10
-alkoxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
8
-C
40
-arylalkenyl group or a C
7
-C
40
-alkylaryl group, or R
11
and R
12
or R
11
and R
13
, in each case with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
8
and R
9
are identical or different and are as defined for R
11
, and
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2.
Alkyl is straight-chain or branched alkyl. Halogen (halogenated) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
In the formula I, M
1
is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
R
1
and R
2
are identical or different and are a hydrogen atom, a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group, a C
1
-C
10
-, preferably C
1
-C
3
-alkoxy group, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, a C
6
-C
10
-, preferably C
6
-C
8
-aryloxy group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl group, a C
7
-C
40
- , preferably C
7
-C
12
-alkylaryl group, a C
8
-C
40
-, preferably C
8
-C
12
-aryl alkenyl group or a halogen atom, preferably chlorine.
R
3
and R
4
are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C
1
-C
10
-, preferably C
1
-C
4
-alkyl group, which may be halogenated, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, an —NR
2
10
, —SR
10
, —OSiR
3
10
, —SiR
3
10
, or PR
2
10
radical in whcih R
10
is a halogen atom, preferably a chlorine atom, or a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group or a C
6
-C
10
-, preferably C
6
-C
8
-aryl group. R
3
and R
4
are particularly preferably hydrogen.
R
5
and R
6
are identical or different, preferably identical, and are as defined for R
3
and R
4
, with the proviso that R
5
and R
6
cannot be hydrogen. R
5
and R
6
are preferably (C
1
-C
4
)-alkyl, which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl, in particular methyl.
═BR
11
, ═AlR
11
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
11
, ═CO, ═Pr
11
or ═P(O)R
11
, where R
11
, R
12
and R
13
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-, preferably C
1
-C
4
-alkyl group, in particular a methyl group, a C
1
-C
10
-fluoroalkyl group, preferably a CF
3
group, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, a C
6
-C
10
-fluoroaryl group, preferably a pentafluorophenyl group, a C
1
-C
10
-, preferably C
1
-C
4
-alkoxy group, in particular a methoxy group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl group, a C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl group or a C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl group, or R
11
and R
12
or R
11
and R
13
, in each case together with the atoms connecting them, form a ring.
M
2
is silicon, germanium or tin, preferably silicon or germanium.
R
7
is preferably ═CR
11
R
12
, ═SiR
11
R
12
, ═GeR
11
R
12
, —O—, —S—, ═SO, ═PR
11
or ═P(O)R
11
.
R
8
and R
9
are identical or different and are as defined as for R
11
.
m and n are identical or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
The particularly preferred metallocenes are thus those in which, in the formula I, M
1
is Zr or Hf, R
1
and R
2
are identical or different and are methyl or chlorine, R
3
and R
4
are hydrogen, R
5
and R
6
are identical or different and are methyl, ethyl or trifluoromethyl, R
7
is a
radical, and n plus m is zero or 1; in particular the compounds I listed in the working examples.
Of the compounds I mentioned in the working examples, rac-dimethylsilyl(2-methyl-1-indenyl)
2
zirconium dichloride, rac-ethylene(2-methyl-1-indenyl)
2
zirconium dichloride, rac-dimethylsilyl(2-methyl-1-indenyl)
2
dimethylzirconium and rac-ethylene(2-methyl-1-indenyl)
2
dimethylzirconium are particularly important.
The chiral metallocenes are employed as racemates for the preparation of highly isotactic poly-1-olefins. However, it is also possible to use the pure R- or S-form. These pure stereoisomeric forms allow the preparation of an optically active polymer. However, the meso form of the metallocenes should be separated off since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to mirror symmetry at the central metal, and it is therefore not possible to produce a highly isotactic polymer. If the meso form is not separated off, atactic polymer is formed alongside isotactic polymers. For certain applications—soft moldings for example—this may be entirely desirable.
The principle of resolution of the stereoisomers is known.
The present invention furthermore provides a process for the preparation of the metallocenes I, which comprises reacting a compound of the formula II
where R
3
-R
9
, m and n are as described in the formula I, and M
3
is an alkali metal, preferably lithium,
a) with a compound of the formula III
M
1
X
4
  (III)
in which M
1
is as defined in the formula I, and X is a halogen atom, preferably chlorine, or
b) with a compound of the formula IIIa
M
1
X
4
L
2
  (IIIa)
in which M
1
and X are as defined above, and L is a donor ligand,
and, if desired, derivatizing the resultant reaction product.
Examples of suitable donor li

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