Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1999-02-10
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, C502S117000, C526S160000, C526S943000, C526S352000, C526S127000
Reexamination Certificate
active
06444606
ABSTRACT:
The present invention relates to substituted metallocenes and highly active supported catalyst systems which can advantageously be used in olefin polymerization, and to a process for their preparation and also to polymers which are prepared using the supported catalyst systems.
Processes for preparing polyolefins using soluble, homogeneous catalyst systems comprising a transition metal component of the metallocene type and a cocatalyst component of the type of an aluminoxane, a Lewis acid or an ionic compound are known. These catalysts have a high activity and give polymers and copolymers having a narrow molar mass distribution.
In polymerizations using soluble, homogeneous catalyst systems, heavy deposits are formed on reactor walls and the stirrer if the polymer is obtained as a solid. These deposits are formed by agglomeration of the polymer particles whenever metallocene and/or cocatalyst are present in dissolved form in the suspension. The deposits in the reactor systems quickly reach considerable thicknesses and have a high strength. They prevent heat exchange to the cooling medium and therefore have to be removed regularly. Such homogeneous catalyst systems cannot be used industrially in the liquid monomer or in the gas phase.
To avoid deposit formation in the reactor, supported catalyst systems in which the metallocene and/or the aluminum compound serving as cocatalyst is/are fixed on an inorganic support material have been proposed.
EP-A-0 576 970 discloses metallocenes and corresponding supported catalyst systems.
At industrially relevant polymerization temperatures of from 50° C. to 80° C., the supported catalyst systems give polymers, in particular polypropylenes, having melting points of at most 156° C. Typical values for such systems are merely in the region of 150° C. For many polymer applications, for example extrusion and injection molding, such products are not satisfactory in respect of hardness and mechanical strength.
It is an object of the present invention to provide supported etallocene catalysts which, owing to their high regiospecificity and stereospecificity, give polymers having a higher melting point under industrially relevant polymerization conditions and provide an environmentally friendly and economical process for preparing the polymers.
We have found that this object is achieved by a supported catalyst system comprising at least one specifically substituted metallocene, at least one cocatalyst, at least one passivated support and, if desired, at least one further additive component. According to the present invention, the catalyst system is prepared by mixing at least one specifically substituted metallocene, at least one cocatalyst and at least one passivated support.
As metallocene component of the catalyst system of the present invention, use is made of at least one compound of the formula I below,
where
M
1
is metal of group IVb of the Periodic Table of the Elements,
R
1
and R
2
are identical or different and are each a hydrogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
20
-aryl group, a C
6
-C
10
-aryloxy group, a C
2
-C
10
-alkenyl group, an OH group, an NR
12
2
group, where R
12
is a C
1
-C
10
-alkyl group or C
6-C
14
-aryl group, or a halogen atom,
R
3
, R
4
, R
6
, R
7
, R
8
and also R
3
′, R
4
′, R
6
′, R
7
′ and R
8
′ are identical or different and are each a hydrogen atom, a hydrocarbon group which may be halogenated, linear, cyclic or branched, for example a C
1
-C
10
-alkyl group, C
2
-C
10
-alkenyl group, C
6-C
20
-aryl group, a C
7
-C
40
-arylalkyl group, a C
7-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, with the proviso that R
3
and R
3
′ are not hydrogen, and
R
5
and R
5
′ are identical or different and are each a C
6-C
40
-aryl group which in the para position to the bonding position on the indenyl ring bears a substituent R
13
where x, y=0, 1 and x+y=0, 1 or 2, where the aromatic ring system x and/or the aromatic ring system y can also be linked to the radicals R
6
, R
6
, or R
4
, R
4
′, and R
13
is a C
2
-C
20
-alkyl radical, a C
2
-C
20
-alkenyl radical, a C
6
-C
24
-aryl radical, a C
7
-C
40
-arylalkyl radical, a C
7
-C
40
-alkylaryl radical, a C
8
-C
40
-arylalkenyl radical, where the hydrocarbon radicals may also be halogenated or partially halogenated by fluorine, chlorine or bromine, —NR
2
14
, —PR
2
14
, —SR
14
, —OR
14
, —SiR
3
14
, —NR
3
14
or —PR
3
14
, where R
14
is as defined for R
3
,
R
9
is a bridge
where
R
10
and R
11
, even when bearing the same index, can be identical or different and are each a hydrogen atom, a halogen atom or a C
1-C
40
-group such as a C
1
-C
20
-alkyl group, a C
1
-C
10
-fluoroalkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
14
-aryl group, a C
6
-C
10
-fluoroaryl 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
-alkylaryl group or a C
8
-C
40
-arylalkenyl group or R
10
and R
11
together with the atoms connecting them form one or more rings, z is an integer from zero to 18 and M
2
is silicon, germanium or tin, and
R
9
may also link two units of the formula I to one another.
The 4,5,6,7-tetrahydroindenyl analogues corresponding to the compounds I are likewise of importance.
In formula I, it is preferred that
M1 is zirconium, hafnium or titanium,
R
1
and R
2
are identical and are methyl or chlorine,
R
3
and R
3
′, are identical or different and are each a hydrocarbon group which may be halogenated, linear, cyclic or branched, for example a C
1
-C
10
-alkyl group, C
2-C
10
-alkenyl group or a C
7
-C
40
-alkylaryl group,
R
9
is R
10
R
11
Si═, R
10
R
11
Ge═, R
10
R
11
C═ or —(R
10
R
11
C-CR
10
R
11
)—, where R
10
and R
11
are identical or different and are each a C
1
-C
20
-hydrocarbon group, in particular C
1
-C
10
-alkyl or C
6
-C
14
-aryl,
R
5
and R
5
′ are preferably identical or different and are each a C
6
-C
20
-aryl group which in the para position to the bonding position to the indenyl ring bears a substituent R
13
,
where x, y=0, 1 and x+y=0, 1 or 2 and
R
13
is a C
2-C
10
alkyl radical, a C
2-C
10
-alkenyl radical, a C
6
-C
18
-aryl radical, a C
7
-C
20
-arylalkyl radical, a C
7
-C
20
-alkylaryl radical, a C
8
-C
20
-arylalkenyl radical, where the hydrocarbon radicals may also be halogenated or partially halogenated by fluorine or chlorine, —NR
2
14
, —PR
2
14
, —SR
14
, —SiR
3
14
, —NR
3
14
or —PR
3
14
, where R
14
is as defined for R
3
.
In formula I, it is very particularly preferred that
M
1
is zirconium,
R
1
and R
2
are identical and are methyl or chlorine, in particular chlorine,
R
9
is R
10
R
11
Si═, R
10
R
11
C═ or —(R
10
R
11
C-CR
10
R
11
)—, where R
10
and R
11
are identical or different and are hydrogen, phenyl, methyl or ethyl,
R
4
, R
6
, R
7
and R
8
and also R
4
′, R
6
′, R
7
′ and R
8
′ are hydrogen, and
R
5
and R
5
′ are identical or different and are each a C
6
-C
20
-aryl group, in particular a phenyl, naphthyl or anthracenyl group, which in the para position to the bonding position to the indenyl ring bears a substituent R
13
, where R
13
is an SiR
3
14
radical, where R
14
is as defined for R
3
or is a branched C
3
-C
10
alkyl radical, a C
2
-C
10
-alkenyl radical or a branched C
7
-C
20
-alkylaryl radical, where the hydrocarbon radicals may also be halogenated or partially halogenated by fluorine or chlorine.
Preferred metallocene components of the catalyst system of the present invention are combinations of the following molecular fragments of the compound I
M
1
R
1
R
2
is ZrCl
2
, Zr(CH
3
)
2
,
R
3
,R
3
′ are methyl, ethyl, isopropyl, isobutyl, n-butyl, s-butyl,
R
4
,R
8
,R
4
′,R
8
′ are hydrogen,
R
6
,R
7
,R
6
′,R
7
′ are hydrogen, C
1-C
4
-alkyl, C
6
-C
10
-aryl,
R
5
and R
5
′ are p-isopropylphenyl, p-tert-butylphenyl, p-s-butyl-phenyl, p-cyclohexyl, p-trimethylsilylphenyl, p-adamantylphenyl, p-(F
3
C)
3
C-phenyl
R
9
Bingel Carsten
Fraaije Volker
Goeres Markus
Winter Andreas
Basell Polypropylen GmbH
Keil & Weinkauf
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