Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-09-14
2003-06-24
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...
C526S129000, C526S160000, C526S161000, C526S943000, C526S113000, C502S103000, C502S117000, C502S152000, C502S162000
Reexamination Certificate
active
06583238
ABSTRACT:
The present invention relates to catalyst systems comprising specifically substituted metallocenes which can advantageously be used in olefin polymerization and to a process for preparing them and also to their use in the polymerization of olefins.
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 form on reactor walls and stirrer if the polymer is obtained as a solid. These deposits are always formed by agglomeration of the 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 rapidly 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 in 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 are fixed to an inorganic support material have been proposed.
EP-A-0,576,970 discloses metallocenes and corresponding supported catalyst systems.
However, a frequent problem in the industrial use of supported catalyst systems is the leaching of the metallocene component from the support material, which results, for example, in undesirable deposit formation in the reactor.
It is an object of the present invention to find novel catalyst systems in which the metallocene component can be firmly fixed to the support and cannot be leached from the support material under industrially relevant polymerization conditions.
We have found that this object is achieved by catalyst systems comprising at least one specifically substituted metallocene which contains a cationic group as substituent.
The present invention provides a catalyst system comprising
a) at least one support,
b) at least one cocatalyst and
c) at least one metallocene of the formula (I)
where
M
1
is a transition metal of Group 4 of the Periodic Table of the Elements, for example titanium, zirconium or hafnium, preferably zirconium,
R
1
and R
2
are identical or different and are each a hydrogen atom, a C
1
-C
20
group, preferably a C
1
-C
20
-alkyl group, a C
6
-C
14
-aryl group, a C
2
-C
20
-alkenyl group, a C
2
-C
20
-alkynyl group, or a C
7
-C
20
-alkylaryl group, each of which may bear one or more identical or different halogen atoms as substituents, a halogen atom, an —SiMe
3
group or an OSiMe
3
group, particularly preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, branched pentyl, n-hexyl, branched hexyl, cyclohexyl or benzyl,
R
3
are identical or different and are each a hydrogen atom or a C
1
-C
40
group, preferably a C
1
-C
20
-alkyl group which may be substituted, in particular methyl, ethyl, trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, cyclopropyl, cyclopentyl or cyclohexyl, a C
6
-C
14
-aryl group which may be substituted, for example phenyl, tolyl, xylyl, tert-butylphenyl, ethylphenyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, methoxyphenyl, fluorophenyl, dimethylaminophenyl, trimethylammoniumphenyl iodide, dimethylsulfoniumphenyl bromide, triethylphosphoniumphenyl triflate, naphthyl, acenaphthyl, phenanthrenyl or anthracenyl, a C
2
-C
20
-alkenyl group, a C
2
-C
20
-alkynyl group, a C
7
-C
20
-alkylaryl group, a halogen atom, an SiMe
3
group, an OSiMe
3
group or a C
1
-C
20
-heterocyclic group which may be substituted, where the term heteroatom encompasses all elements with the exception of carbon and hydrogen and preferably refers to an atom of group 14, 15 or 16 of the Periodic Table of the Elements, and two radicals R
3
may form a monocyclic or polycyclic ring system which may in turn be substituted, where at least one of the radicals R
1
, R
2
, R
3
is a cationic group (—DE
L
)
+
Y
−
,
where
D is an atom of group 15 or 16 of the Periodic Table of the Elements, preferably nitrogen, phosphorus, oxygen or sulfur,
E are identical or different and are each a hydrogen atom, a C
1
-C
20
group, preferably a C
1
-C
20
-alkyl group, a C
6
-C
14
-aryl group, a C
2
-C
20
-alkenyl group, a C
2
-C
20
-alkynyl group or a C
7
-C
20
-alkylaryl group, a trialkylsilyl group, a triarylsilyl group or an alkylarylsilyl group, which may each be substituted, and two radicals E may form a monocyclic or polycyclic ring system which may in turn be substituted, particularly preferably a hydrogen atom, methyl, ethyl, propyl, butyl, allyl, benzyl, methoxymethyl, benzyloxymethyl, 2-methoxyethoxymethyl, 2-trimethylsilylethoxymethyl or trimethylsilyl,
L is 3 when D is an atom of group 15 of the Periodic Table of the Elements and is 2 when D is an atom of group 16 of the Periodic Table of the Elements,
Y is halogen, C
1
-C
10
-alkylsulfonate, C
1
-C
10
-haloalkylsulfonate, C
6
-C
20
-arylsulfonate, C
6
-C
20
-haloarylsulfonate, C
7
-C
20
-alkylarylsulfonate, C
1
-C
20
-haloalkylcarboxylate, C
1
-C
10
-alkylsulfate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate or hexafluoroarsenate, preferably chloride, bromide, iodide, triflate, mesylate, tosylate, benzenesulfonate, trifluoroacetate, methyl sulfate, tetrafluoroborate or hexafluorophosphate,
m is an integer less than or equal to 4 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1,
m′ is an integer less than or equal to 4 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1,
k is zero or 1, with the metallocene being unbridged when k=0 and the metallocene being bridged when k=1,
A is a bridge of the formula
or ═BR
4
, AlR
4
, —S—, —SO—, —SO
2
—, ═NR
4
, ═PR
4
, ═P(O)R
4
, o-phenylene or 2,2′-biphenylene, where
M
2
is carbon, silicon, germanium, tin, nitrogen or phosphorus, preferably carbon, silicon or germanium, in particular carbon or silicon,
o is 1, 2, 3 or 4, preferably 1 or 2,
R
4
and R
5
are identical or different and are each, independently of one another, a hydrogen atom, halogen, a C
1
-C
20
group, preferably a C
1
-C
20
-alkyl, in particular methyl, a C
6
-C
14
-aryl, in particular phenyl or naphthyl, a C
1
-C
10
-alkoxy, a C
2
-C
10
-alkenyl, a C
7
-C
20
-arylalkyl, a C
7
-C
20
-alkylaryl, a C
6
-C
10
-aryloxy, a C
1
-C
10
-fluoroalkyl, a C
6
-C
10
-haloaryl, a C
2
-C
10
-alkynyl, a C
3
-C
20
-alkylsilyl, in particular trimethylsilyl, triethylsilyl or tert-butyidimethylsilyl, a C
3
-C
20
-arylsilyl, in particular triphenylsilyl, or a C
3
-C
20
-alkylarylsilyl, in particular dimethylphenylsilyl, diphenylsilyl or diphenyl-tert-butylsilyl, and R
4
and R
5
may form a monocyclic or polycyclic ring system.
A is preferably dimethylsilanediyl, dimethylgermanediyl, ethylidene, methylethylidene, 1,1-dimethylethylidene, 1,2-dimethylethylidene, tetramethylethylidene, isopropylidene, phenylmethylmethylidene or diphenylmethylidene, particularly preferably dimethylsilanediyl or ethylidene.
The radicals X are identical or different and are each a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a C
1
-C
10
-alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl or cyclohexyl, a C
6
-C
15
-aryl group such as phenyl or naphthyl, a C
1
-C
10
-alkoxy group such as methoxy, ethoxy or tert-butoxy, a C
6
-C
15
-aryloxy group or a benzyl group, preferably a chlorine atom, a fluorine atom, a methyl group or a benzyl group, particularly preferably a chlorine atom or a methyl group.
Particularly preferred metallocenes of the formula (I) have the formula (I*),
where
M
1
,
Bohnen Hans
Göres Markus
Basell Polyolefine GmbH
Cheung William
Keil & Weinkauf
Wu David W.
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