Catalyst solution for the polymerization of &agr;-olefins

Details Catalyst solution for the polymerization of &agr;-olefins Catalyst solution for the polymerization of &agr;-olefins

1999-11-02

2002-09-03

Wu, David W. (Department: 1713)

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

Catalyst or precursor therefor

Organic compound containing

C502S104000, C502S152000, C526S075000, C526S089000, C526S160000, C526S161000, C526S348600, C526S943000

Reexamination Certificate

active

06444607

ABSTRACT:

The present invention relates to a catalyst solution for polymerizing &agr;-olefins, obtainable by
a) reacting a metallocene compound of the formula I
 where the substituents have the following meanings:
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum
X is hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, —OR
6
or —NR
6
R
7
,
where
R
6
and R
7
are C
1
-C
10
-alkyl, C
6
-C
15
-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical,
R
1
to R
5
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C
1
-C
10
-alkyl as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may also together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R
8
)
3
where
R
8
is C
1
-C
10
-alkyl, C
3
-C
10
-cycloalkyl or C
6
-C
15
-aryl,
Z is X or
 where the radicals
R
9
to R
13
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C
1
-C
10
-alkyl as substituent, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals may also together form a saturated or unsaturated cyclic group having from 4 to 15 carbon atoms, or Si(R
14
)
3
where
R
14
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
 or where the radicals R
4
and Z together form an —R
15
—A— group in which
R
15
is
 ═BR
16
, ═AlR
16
, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR
16
, ═CO, ═PR
16
or ═P(O)R
16
,
where
R
16
, R
17
and R
18
are identical or different and are each 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
-fluoroaryl group, a C
6
-C
10
-aryl 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
-alkyl-aryl group or two adjacent radicals together with the atoms connecting them form a ring, and
M
2
is silicon, germanium or tin,
A
 where
R
19
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
3
-C
10
-cycloalkyl, alkylaryl or Si(R
20
)
3
,
R
20
is hydrogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl which may in turn bear C
1
-C
4
-alkyl groups as sub-stituents or C
3
-C
10
-cycloalkyl
or the radicals R
4
and R
12
together form an —R
15
— group,
with an activator compound which can react with the metallocene compound I so as to displace a ligand X from the central atom M and to stabilize the resulting cationic complex by means of a non-coordinating anion as ion pair,
b) adding one or more &agr;-olefins in a molar ratio of metallocene compound I: &agr;-olefin of from 1:1 to 1:100 and
c) mixing with at least 10 parts by volume of an aliphatic hydrocarbon.
The present invention further relates to a process for polymerizing &agr;-olefins in the presence of this catalyst solution and also to the use of this catalyst solution for the polymerization of &agr;-olefins.
The cationic activation of metallocene complexes to form active catalyst compounds has been described in numerous publications. In these reactions, the metallocene complex is reacted with an ion-exchange component, eg. a cation or a Lewis acid which is able to irreversibly react with one of the complexing ligands, and a non-coordinating anion which can stabilize the resulting cationic metallocene complexes. The structure of many metallocene complexes, but in particular the structure of the activating reagents and of the ion pairs of cationic metallocene complex and anionic non-coordinating counterion formed during the course of the activation, makes moderately polar solvents generally necessary for this reaction, for example aromatic or halogenated hydrocarbons. Thus, EP-A-709 393 describes the cationic activation of metallocene complexes having substituted fluorophenyl ligands in toluene as solvent. WO-93/25590 likewise describes the cationic activation of metallocene complexes, with preference being given to using aromatic solvents, in particular toluene (see examples) for these reactions. The linear, branched or alicyclic hydrocarbons which are likewise mentioned for this purpose have generally been found to be unsuitable for this purpose since they have only insufficient solvent capability for, in particular, the cationic metallocene complexes and the activation reagents.
The cationically activated metallocene complexes can also be advantageously used in unsupported form in slurry or solution polymerization processes. Solvents which have been found to be suitable for these polymerization processes, in particular for polymerization processes at high temperature and high pressure, are, in particular, aliphatic solvents, in particular saturated hydrocarbons. In contrast, aromatic and halogenated hydrocarbons have disadvantages which are presumably attributable to their reactivity and to a destruction or blocking of the catalyst by these compounds. In polymerizations in these solvents, a lower catalyst productivity, a greater need for alkyl compounds for eliminating impurities and an increased proportion of wax-like by-products in the polymers are observed. However, the unsatisfactory solubility of cationically activated metallocene catalysts in aliphatic solvents has hitherto usually made the use of aromatic solvents necessary in such solution polymerization processes.
It is an object of the present invention to increase the solubility of cationically activated catalyst complexes so that they have sufficient solubility in aliphatic solvents.
We have found that this object is achieved by the catalyst solution described in the introduction for polymerizing &agr;-olefins, a process for polymerizing &agr;-olefins in the presence of this catalyst solution and the use of this catalyst solution for the polymerization of &agr;-olefins.
Among the metallocene complexes of the formula I, preference is given to
Particular preference is given to those transition metal complexes which have two aromatic ring systems bridged to one another as ligands, ie. in particular the transition metal complexes of the formula Ic.
The radicals X can be identical or different; they are preferably identical.
Among the compounds of the formula Ia, particular preference is given to those in which
M is titanium, zirconium or hafnium,
X is C
1
-C
4
-alkyl or phenyl and
R
1
to R
5
is hydrogen or C
1
-C
4
-alkyl.
Among the compounds of the formula Ib, preference is given to those in which
M is titanium, zirconium or hafnium,
X is C
1
-C
4
-alkyl or phenyl,
R
1
to R
5
is hydrogen, C
1
-C
4
-alkyl or Si(R
8
)
3
,
R
9
to R
13
is hydrogen, C
1
-C
4
-alkyl or Si(R
14
)
3
.
In particular, suitable compounds of the formula Ib are those in which the cyclopentadienyl radicals are identical.
Examples of particularly suitable compounds are, inter alia, those which are derived from the following compounds II:
bis(cyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(ethylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dichloride and
bis(trimethylsilylcyclopentadienyl)zirconium dichloride
and also the corresponding dimethylzirconium compounds.
Particularly suitable compounds of the formula Ic are those in which
R
1
and R
9
are identical and are hydrogen or C
1
-C
10
-alkyl groups,
R
5
and R
13
are identical and are hydrogen, methyl, ethyl, isopropyl or tert-butyl,
R
2
, R
3
, R
10
and R
11
have the meanings: R
3
and R
11
are C
1
-C
4
-alkyl, R
2
and R
10
are hydrogen, or two adjacent radicals R
2
and R
3
or R
10
and R
11
together form a cyclic group having from 4 to 12 carbon atoms,
R
15
is
M is titanium, zirconium or hafnium and
X is C
1
-C
4
-alkyl or phenyl.
Examples of particularly suitable complexes are, inter alia, those which are derived from the following compounds II:
dimethylsilanediylbis(cyclopentadienyl)zirconium

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