Polymerization process using a monocyclopentadienyl compound...

Details Polymerization process using a monocyclopentadienyl compound... Polymerization process using a monocyclopentadienyl compound...

1999-01-28

2001-04-17

Lipman, Bernard (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S127000, C526S129000, C526S134000, C526S161000, C526S172000, C526S943000

Reexamination Certificate

active

06218489

ABSTRACT:

The present invention relates to a transition metal compound and a process for its preparation and also its use as a catalyst component in the preparation of polyolefins.
The preparation of polyolefins using soluble metallocenes or monocyclopentadienyl compounds in combination with aluminoxanes or other cocatalysts which, owing to their Lewis acidity, can convert the neutral transition metal compound into a cation and stabilize it is known from the literature (EP-A 129 368, EP-A 351 392, EP-A 416 815).
Metallocenes and monocyclopentadienyl compounds are of great interest not only in respect of the polymerization or oligomerization of olefins. They can also be used as hydrogenation, epoxidation, isomerization and C—C coupling catalysts (Chem. Rev. 1992, 92, 965-994).
Use of soluble metallocene compounds based on bis(cyclopentadienyl)zirconium dialkyls or dihalides in combination with oligomeric aluminoxanes gives atactic polymers which, owing to their unbalanced and unsatisfactory product properties, are of little industrial importance. In addition, certain olefin copolymers are not obtainable.
Derivatives of zirconocene dichloride in which the two substituted cyclopentadienyl groups are connected to one another via a methylene, ethylene or dimethylsilyl bridge can, owing to their conformational rigidity, be used as catalysts for the isospecific polymerization of olefins (EP-A 316 155).
It is an object of the invention to provide new transition metal compounds.
The present invention accordingly provides a transition metal compound containing as ligands a cyclopentadienyl group and a further &pgr;-bonded unit which are connected to one another via a bridge A.
The transition metal compound of the invention has the formula I,
where M
1
is a metal of group IIIb, IVb or Vb of the Periodic Table of the Elements,
R
1
, R
2
, R
3
and R
4
are identical or diferent and are each a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group such as a C
1
-C
20
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
20
-aryl group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, an —SiR
5
3
, —NR
5
2
, —Si(OR
5
)
3
, —Si(SR
5
)
3
or —PR
5
2
radical, where R
5
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, or two or more radicals R
1
, R
2
, R
3
or R
4
together with the atoms connecting them form a ring system which preferably contains from 4 to 40, particularly preferably from 6 to 20, carbon atoms,
Y are identical or different and are each a hydrogen atom, a C
1
-C
40
-hydrocarbon-containing group such as a C
1
-C
20
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
20
-aryl group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-alkylaryl group, a C
8
-C
40
-arylalkenyl group, or a substituted or unsubstituted butadiene unit, an OH group, a halogen atom or a NR
5
2
group, where R
5
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group,
k is an integer which corresponds to the valence of the transition metal atom M
1
minus two and if Y is a butadiene unit, k is 1,
A is a bridge such as
where n is an integer from 1 to 20, I is an integer from 1 to 20, Z is
SO
2
, O or S, where R
5
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group,
R
6
and R
7
are identical or different and are each a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group such as a C
1
-C
20
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
20
-aryl group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, or in each case two radicals R
6
, in each case two radicals R
7
, or one of each of the radicals R
6
and R
7
in each case together with the atoms connecting them form a ring system and M
2
is silicon, germanium or tin,
R
8
is a hydrogen atom, a halogen atom, a C
1
-C
40
-group such as a C
1
-C
20
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
20
-aryl group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, a —SiR
5
3
, —NR
5
2
, —Si(OR
5
)
3
, —Si(SR
5
)
3
or —PR
5
2
radical, where R
5
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, and
X is an element of group Va or VIa of the Periodic Table of the Elements, where if X is an element of group Va, X bears a radical R
9
which is a hydrogen atom, a halogen atom, a C
1
-C
40
-group such as a C
1
-C
20
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
20
-aryl group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, an —SiR
5
3
, —NR
5
2
, —Si(OR
5
)
3
, —Si(SR
5
)
3
or —PR
5
2
radical, where R
5
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group.
For compounds of the formula I, it is preferred that
M
1
is a metal of group IVb of the Periodic Table of the Elements, for example titanium, zirconium or hafnium,
R
1
, R
2
, R
3
and R
4
are identical or different and are each a hydrogen atom or a C
1
-C
10
-hydrocarbon-containing group such as a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, or two or more radicals R
1
, R
2
, R
3
or R
4
together with the atoms connecting them form a ring system which preferably has from 6 to 10 carbon atoms,
Y are identical and, in particular, are each a C
1
-C
10
-hydrocarbon-containing group such as a C
1
-C
4
-alkyl group or a substituted or unsubstituted, in particular unsubstituted, butadiene unit, or a halogen atom, in particular chlorine,
A is
where n is an integer from 1 to 8, in particular 1, 2, 3 or 4,
R
6
and R
7
are identical or different and are each a hydrogen atom or a C
1
-C
10
-hydrocarbon-containing group such as a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, or in each case two radicals R
6
, in each case two radicals R
7
, or one of each of the radicals R
6
and R
7
in each case together with the atoms connecting them form a hydrocarbon ring system,
R
8
is a C
1
-C
10
-hydrocarbon group such as a C
1
-C
4
-alkyl group or a C
6
-C
10
-aryl group, and
X is an element of group Va, in particular nitrogen or phosphorus, or group VIa, in particular oxygen or sulfur, of the Periodic Table of the Elements,
where if X is an element of group Va, X bears a radical R
9
which is a hydrogen atom, a C
1
-C
10
-hydrocarbon-containing group such as a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group or a —SiR
5
3
, —NR
5
2
, —Si(OR
5
)
3
, —Si(SR
5
)
3
or —PR
5
2
radical, where R
5
are identical or different and are each a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group.
Particular preference is given to compounds of the formula I in which
M
1
is titanium or zirconium,
R
1
, R
2
, R
3
and R
4
are identical or different and are each a hydrogen atom, a C
1
-C
4
-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or a C
6
-C
10
-aryl group such as phenyl or naphthyl, or R
1
and R
2
or R
3
and R
4
or R
2
and R
3
together with the atoms connecting them form an aromatic hydrocarbon ring system, in particular a six-membered ring, which may in turn be substituted,
Y are identical and are, in particular, methyl, phenyl or chlorine,
A is
R
6
and R
7
are identical or different and are each a hydrogen atom, a C
1
-C
4
-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or a C
6
-C
10
-aryl group such as phenyl or naphthyl,
R
8
is a C
1
-C
4
-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or a C
6
-C
10
-aryl group such as phenyl or naphthyl, and
X is nitrogen or oxygen, where if X is nitrogen it bears a radical R
9
which is a hydrogen atom, a C
1
-C
4
-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or a C
6
-C
10
-aryl group such as phenyl or naphthyl, —SiR
5
3
or —Si(OR
5
)
3
, in particular —SiR
5
3
, where R
5
are identical or different and are each a C
1
-C
4
-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobuty

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