Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-03-22
2002-03-05
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...
C526S161000, C526S281000, C526S335000, C526S943000, C526S348600, C502S152000, C502S155000
Reexamination Certificate
active
06353064
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to compounds in which a transition metal is complexed with two ligand systems and the two systems are reversibly connected to one another by at least one bridge comprising a donor and an acceptor.
BACKGROUND OF THE INVENTION
The co-ordination bond formed between the donor atom and the acceptor atom produces a positive (partial) charge in the donor group and a negative (partial) charge in the acceptor group:
The invention also relates to the use of these supported catalysts with a donor-acceptor interaction as polymerization catalysts.
Metallocenes as &pgr;-complex compounds and their use as catalysts in the polymerization of olefins have been known for a long time (EP-A-129,368 and the literature cited therein). Furthermore, it is known from EP-A-129,368 that metallocenes in combination with aluminum alkyl/water as co-catalysts form effective systems for the polymerization of ethylene (for example, methyl aluminoxane=MAO is formed from ca. 1 mole of trimethyl aluminum and 1 mole of water. Other stoichiometric ratios have already also been successfully employed (WO 94/20506)). Also, metallocenes are already known in which cyclopentadienyl skeletons are covalently joined to one another by a bridge. As an example of the numerous patents and patent applications in this field, EP-A 704,461 may be mentioned, in which the linkage group mentioned therein is a (substituted) methylene group or ethylene group, a silylene group, a substituted silylene group, a substituted germylene group, or a substituted phosphine group. Also, in EP-A 704,461 the bridged metallocenes are provided as polymerization catalysts for olefins.
Catalysts with a donor-acceptor interaction and their use as polymerization catalysts are known in principle.
For example, WO-A-98/01455 describes compounds in which a transition metal is complexed with two &pgr;-systems, and more particularly with aromatic &pgr;-systems (metallocenes) and the two systems are reversibly connected to one another by means of a bridge comprising a donor and an acceptor, the donor and acceptor atoms being bonded as substituents to the &pgr;-systems, as well as their use as polymerization catalysts.
WO-A-98/01745 describes compounds in which a transition metal is complexed with two &pgr;-systems, and more particularly with aromatic &pgr;-systems (metallocenes), and the two systems are reversibly connected to one another by means of a bridge comprising a donor and an acceptor, at least one of the donor and/or acceptor atoms being part of the in each case respective &pgr;-system, as well as their use as polymerization catalysts.
The earlier application PCT/EP 98/08074 describes compounds in which a transition metal is complexed with a &pgr;-system and which exhibit a donor-acceptor interaction, either the donor group or the acceptor group being bonded to the transition metal, as well as their use as polymerization catalysts.
The patent applications WO-A-98/01483 to WO-A-98/01487, as well as the earlier application PCT/EP 98/08012, describe industrial polymerization processes using the described catalysts with a donor-acceptor interaction.
It is known from these documents that the catalysts with a donor-acceptor interaction can be used in supported form.
However, it was surprising to the person skilled in the art that particularly advantageous supported catalysts with a donor-acceptor interaction can be produced if special clays are used as support material.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a composition containing:
a) a transition metal compound with at least one donor-acceptor interaction
b) an ion-exchanging support material with a layer lattice structure, and optionally
c) one or more co-catalysts.
DETAILED DESCRIPTION OF THE INVENTION
Suitable as component a) are the transition metal compounds with a donor-acceptor interaction described in the applications WO-A-98/01455, WO-A-98/01745, WO-A-98/01483 to WO-A-98/01487, as well as the compounds described in the earlier applications PCT/EP 98/08074 and PCT/EP 98/08012.
Particularly suitable are metallocene compounds of the formulae
in which CpI and CpII represent two identical or different carbanions with a cyclopentadienyl-containing structure, in which one to all of the H atoms may be replaced by identical or different radicals from the group comprising linear or branched C
1
-C
20
alkyl, which may be singly to completely substituted by halogen, singly—triply substituted by phenyl as well as singly—triply substituted by vinyl, C
6
-C
12
aryl, halogenated aryl with 6 to 12 C atoms, organometallic substituents such as silyl, trimethylsilyl, ferrocenyl, as well as singly or doubly substituted by D and A.
D denotes a donor atom that may additionally carry substituents and that in its respective bonding state has at its disposal at least one free electron pair,
A denotes an acceptor atom that may additionally carry substituents and that in its respective bonding state has an electron pair vacancy,
D and A being coupled to one another by a reversible co-ordination bond in such a way that the donor group adopts a positive (partial)charge and the acceptor group adopts a negative (partial)charge,
M denotes a transition metal of subgroup III, IV, V or VI of the Mendeléeff periodic system, including the lanthanides and actinides,
X denotes an anion equivalent, and
n denotes the number 0, 1, 2, 3 or 4 depending on the charge of M.
The first and the second carbanion CpI and CpII with a cyclopentadienyl skeleton may be the same or different. The cyclopentadienyl skeleton may for example be a skeleton from the group comprising cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene. There may be 1 to 4 substituents per cyclopentadiene ring and/or fused benzene ring. These substituents may be C
1
-C
20
alkyl such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, eicosyl, C
1
-C
20
alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy or iso-butoxy, hexoxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, halogen such as fluorine, chlorine or bromine, C
6
-C
12
aryl such as phenyl, C
1
-C
4
alkylphenyl such as tolyl, ethylphenyl, (i-)propylphenyl, (i-tert.)butylphenyl, xylyl, halogenated phenyl such as fluorophenyl, chlorophenyl or bromophenyl, naphthyl or biphenylyl, triorganyl-silyl such as trimethylsilyl (TMS), ferrocenyl as well as D or A as defined above. Furthermore, fused aromatic rings may be partially or completely hydrogenated so that only the double bond remains, which the fused ring as well as the cyclopentadiene ring both share. Furthermore, benzene rings such as in indene or fluorene may contain one or two fused further benzene rings. Also, the cyclopentadiene and/or cyclopentadienyl ring and a fused benzene ring may jointly contain a further fused benzene ring. Such cyclopentadiene skeletons, in the form of their anions, are excellent ligands for transition metals, each cyclopentadienyl carbanion of the aforementioned, optionally substituted form, compensating a positive charge of the centrally located metal in the complex. Individual examples of such carbanions include: cyclopentadienyl, methyl-cyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, indenyl, phenylindenyl, 1,2-diethyl-cyclopentadienyl, tetramethyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl, &bgr;-phenylpropyl-cyclopentadienyl, tetrahydroindenyl, propyl-cyclopentadienyl, t-butyl-cyclopentadienyl, benzyl-cyclo-pentadienyl, diphenylmethyl-cyclopentadienyl, trimethylgermyl-cyclopentadienyl, trimethylstannyl-cyclopentadienyl, trifluoromethyl-cyclopentadienyl, trimethylsilyl-cyclopentadienyl, pentamethyl-cyclopentadienyl, fluorenyl, tetrahydro-fluorenyl or octahydro-fluorenyl, fluorenyls and indenyls benzo-anellated on the 6-membered ring, N,N-dimethylamino-cyclopentadienyl, dimethylphosphino-cyclopentadienyl, methoxy-cyc
Bayer Aktiengesellschaft
Cheung Noland J.
Gil Joseph C.
Harlan R.
Wu David W.
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