Metallocene compound and polymerization catalyst comprising...

Details Metallocene compound and polymerization catalyst comprising... Metallocene compound and polymerization catalyst comprising...

2000-09-14

2002-10-22

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...

C526S160000, C526S161000, C526S170000, C526S172000, C526S943000, C502S117000, C502S118000, C502S152000, C502S154000, C502S155000, C556S018000, C556S019000, C556S020000, C556S053000

Reexamination Certificate

active

06469114

ABSTRACT:

The present invention relates to specifically substituted metallocenes and corresponding highly active supported catalyst systems which can advantageously be used in olefin polymerization and to a process for preparing them and also to polymers which are prepared using the supported catalyst systems. Processes for preparing polyolefins with the aid of soluble, homogeneous catalyst systems comprising a transition metal component of the metallocene type and a cocatalyst component such as 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 polymerization processes using soluble, homogeneous catalyst systems, thick deposits are formed on reactor walls and stirrer when the polymer is obtained as a solid. These deposits are always formed by agglomeration of polymer particles when metallocene and/or cocatalyst are present in dissolved form in the suspension. Such deposits in the reactor systems have to be removed regularly, since they quickly reach considerable thicknesses, have a high strength and prevent heat transfer to the cooling medium. Such homogeneous catalyst systems cannot be used industrially in modern polymerization processes, for example 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 compounds serving as cocatalyst are fixed on an inorganic support material have been proposed.
EP-A 0 576 970, EP-A 0 659 756 and EP-A 0 659 757 disclose metallocenes and corresponding supported catalyst systems.
To reduce residual catalyst contents in the polymer and for cost reasons, an improvement in the catalyst activities is desirable.
Increasing the loading of the support with active substances (metallocene component(s), cocatalyst(s) and possibly additives) enables the catalyst activities to be increased, but such catalysts at the same time tend to form thick deposits and cannot be used industrially.
It is an object of the present invention to provide specific metallocenes and supported metallocene catalyst systems which make deposit-free polymerization possible under industrially relevant polymerization conditions and give polymers having a high melting point and a high molar mass, even at a high catalyst activity, i.e. high loading with active substances.
We have found that this object is achieved by a specifically substituted metallocene, a supported catalyst system comprising at least one specifically substituted metallocene, at least one cocatalyst, at least one support and, if desired, at least one further additive component.
The catalyst system is prepared according to the present invention by mixing at least one specifically substituted metallocene, at least one cocatalyst and at least one support and, if desired, at least one further additive component.
The metallocene of the present invention, which is also used as metallocene component in the catalyst system of the present invention, is a compound of the formula I below,
where
M
1
is a 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 a C
6
-C
14
-aryl group, or a halogen atom,
R
3
, R
4
, R
6
, R
7
and R
8
and R
3′
and R
4′
are identical or different and are each a hydrogen atom, a hydrocarbon group having from 1 to 40 carbon atoms which may be partially halogenated, halogenated, linear, cyclic or branched, e.g a C
1
-C
10
-alkyl group, a C
2
-C
10
-alkyl group, a 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, an Si(R
13
)
3
group, and N(R
13
)
2
group, or SR
13
group or an OR
13
group, where R
13
is as defined for R
4
with the proviso that R
3
is not hydrogen, where R
3′
and R
4′
may also be joined to form a ring, and
R
5
is a C
6
-C
40
-aryl group which bears a substituent R
14
in the para position relative to the point of linkage to the indenyl
where
R
14
is a halogen atom F, Cl or Br, a C
1
-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, —N(R
15
)
2
, —P(R
15
)
2
, —SR
15
, —OR
15
, —Si(R
15
)
3
, —[N(R
15
)
3
]
+
or —[P(R
15
)
3
]
+
, where R
15
is as defined for R
4
, the radicals R
16
can be identical or different despite having the same index and are hydrogen or as defined for R
14
and any two adjacent radicals R
16
may also be joined to form a ring, or one or more of the radicals R
16
together with the radicals R
6
or R
4
and/or R
14
form a ring, with the proviso that R
14
may also be hydrogen when at least one of the radicals R
16
is different from hydrogen,
R
9
is a bridge
where
R
10
, R
11
can be identical or different, even when having the same index, and are each a hydrogen atom, a halogen atom, a heteroatom-containing C
1
-C
40
-hydrocarbon group or a C
1
-C
40
-hydrocarbon group, for example a C
l
-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, a C
8
-C
40
-arylalkenyl group, —N(R
17
)
2
, —P(R
17
)
2
, —SR
17
, —OR
17
, —SiR
3
7
, —[N(R
17
)
3
]
+
or —[P(R
17
)
3
]
+
where R
17
is as defined for R
4
, or R
10
and R
11
in each case together with the atoms connecting them form one or more rings,
x is an integer from 0 to 18,
M
2
is silicon, germanium or tin, where heteroatom-containing hydrocarbon groups are hydrocarbons which contain at least one element of groups 13 to 16 of the Periodic Table of the Elements, and
R
9
may also link two units of the formula I to one another, and
R
a
is a saturated or unsaturated hydrocarbon group, preferably having from 1 to 40 carbon atoms, in particular from 1 to 30 carbon atoms, which may also be substituted by one or more radicals as defined for R
3
, where the radical R
a
as such contains at least one heteroatom from groups 13, 14, 15 or 16 of the Periodic Table of the Elements.
The above definition of R
a
implies that the heteroatom is present as part of the ring system. Should the ring system already include at least one heteroatom, then one or more radicals R
3
can also contain a heteroatom.
The 4,5,6,7-tetrahydroindenyl analogues corresponding to the compounds of the formula I are likewise of importance.
In formula I, it is preferred that
M
1
is zirconium, hafnium or titanium,
R
1
and R
2
are identical and are methyl, dimethylamine, dibenzyl or chlorine,
R
3
and R
3′
are identical or different and are each a hydrocarbon group which may be partially halogenated, halogenated, linear, cyclic or branched, e.g. a C
1
-C
10
-alkyl group, a 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 hydrogen or a C
1
-C
20
-hydrocarbon group, in particular C
1
-C
10
-alkyl or C
6
-C
14
-aryl,
R
5
is a C
6
-C
20
-aryl group which bears a substituent R
14
in the para position relative to the point of linkage to the indenyl ring, and
R
14
is a C
1
-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 and/or chlorine, —NR
2
15
, —P(R
15
)
2
, —SR
15
,

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