Stock material or miscellaneous articles – Coated or structually defined flake – particle – cell – strand,... – Rod – strand – filament or fiber
Reexamination Certificate
2000-09-18
2002-02-12
Acquah, Samuel A. (Department: 1711)
Stock material or miscellaneous articles
Coated or structually defined flake, particle, cell, strand,...
Rod, strand, filament or fiber
C528S392000, C568S017000, C524S701000, C524S706000, C524S709000, C524S711000, C524S712000, C524S714000, C524S742000, C524S745000, C502S152000, C502S154000, C502S158000, C502S159000, C502S162000, C502S164000, C502S168000, C502S169000
Reexamination Certificate
active
06346324
ABSTRACT:
The present invention relates to cis-bridged metal complexes of the formula (I)
where:
R
5
is an electron-withdrawing radical,
M is a metal of group VIIIB of the periodic table of the elements,
E
1
, E
2
are each an element of group VA of the periodic table of the elements,
z is nitrogen or phosphorus,
R
1
to R
4
are substituents selected, independently of one another, from the group consisting of C
1
-C
20
-organocarbon and C
3
-C
30
-organosilicon radicals in substituted and unsubstituted form,
A′, B′ are C
1
-C
4
-alkylene units in substituted or unsubstituted form, silylene-bridged organic radicals or NR
6
radicals,
R
6
is hydrogen or a substituent selected from the group consisting of C
1
-C
20
-organocarbon and C
3
-C
30
-organosilicon radicals, and
L
1
,L
2
are formally charged ligands.
Furthermore, the present invention relates to a process for preparing such metal complexes and also to their use as essential constituents of catalyst systems for the copolymerization of carbon monoxide with olefinically unsaturated compounds.
In addition, the present invention relates to catalyst systems comprising, as active constituents, a) a cis-bridged metal complex of the formula (I) and b) one or more Lewis acids or protic acids or a mixture of Lewis acids and protic acids. The present invention also relates to processes for the preparation of copolymers of carbon monoxide and olefinically unsaturated monomer compounds and also to the use of catalyst systems based on cis-bridged metal complexes of the formula (I) for the preparation of copolymers of carbon monoxide and olefinically unsaturated monomer compounds. Finally, the invention relates to the use of the copolymers obtained according to the invention and also for the production of fibers, sheets, moldings and coatings said fibers, sheets, moldings and coatings.
Catalyst systems for the preparation of copolymers of carbon monoxide and olefinically unsaturated compounds are known. Active catalyst constituents used are generally cis-palladium complexes chelated by bidentate phosphine ligands such as [Pd(R
2
P(CH
2
)
n
PR
2
)(OAc)
2
] (cf. EP 0 121 965). Ligands which have been found to be particularly useful for the copolymerization of carbon monoxide with ethylene and/or propylene are bidentate phosphine ligands having a propylene bridge, with preference being given to using catalyst systems comprising, for example, [(dmppp)Pd(OAc)
2
](BF
4
)
2
as metal complex (dmppp=1,3-bis{di-(2-methoxyphenyl)phosphino}propane) (cf. J. Organomet. Chem. 417 (1991), 235 ff).
However, the preparation of suitable ligand systems such as 1,3-bis{di(2-methoxyphenyl)phosphino}propane) or 1,3-bis{diphenylphosphino}propane (dppp) requires the handling of extremely reactive and also extremely flammable and toxic compounds. The preparation of, for example, alkylene-bridged phosphine ligands therefore usually requires high investment in terms of equipment. In particular, an industrial-scale preparation is not unproblematical for safety reasons. Furthermore, unsymmetrically substituted alkylene-bridged ligands, i.e. those having different phosphine substituents or containing different chelating atoms, are only obtainable to a limited extent from dibromo- or dichloro-terminated alkylene compounds. In addition, structural analogs of said chelating ligands, even those which differ only slightly from a known structure, are frequently not obtainable by the same or similar route but require a complicated, individual synthesis.
German Patent Applications 19651685.4 and 19651786.9 describe cis-bridged metal complexes or catalyst systems based on these complexes, respectively, which remedy the problems described above. In particular, the complexes used feature an amino or phosphino functionality integrated in the bidentate chelating ligands. These systems are also suitable for covalent linking to a support material.
The abovementioned systems have the disadvantage that it is not always possible to maintain a constant catalyst activity at extended reaction times, in particular when the copolymerization is carried out at elevated temperature.
It is an object of the present invention to provide metal complexes or catalyst systems which are based on these complexes for the copolymerization of carbon monoxide copolymers and which will have consistently high catalyst activity, even under prolonged polymerization times, without losing the advantages of nitrogen- or phosphorus-bridged ligand systems, and will provide good yields in a reproducible manner.
We have found that this object is achieved by the cis-bridged metal complexes defined at the beginning. We have also found a process for the preparation of these metal complexes and also the use of the metal complexes (I) defined as essential constituents of catalyst systems suitable for copolymerizing carbon monoxide and olefinically unsaturated compounds.
The invention also provides catalyst systems comprising, as active constituents, a) a cis-bridged metal complex of the formula (I) and b) one or more Lewis acids or protic acids or a mixture of Lewis acids and protic acids, processes for the preparation of copolymers of carbon monoxide and olefinically unsaturated monomer compounds and also the use of catalyst systems based on cis-bridged metal complexes for the preparation of copolymers of carbon monoxide and olefinically unsaturated monomer compounds. Furthermore, the invention provides the use of the copolymers obtained according to the invention for the preparation of fibers, sheets, moldings and coatings and also said fibers, sheets, moldings and coatings.
Suitable metals M in the metal complexes of the present invention are the metals of group VIIIB of the periodic table of the elements, i.e. iron, cobalt and particularly nickel, and especially the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum and very particularly palladium. In the metal complexes, the metals can be present in formally uncharged, formally singly positively charged or preferably formally doubly positively charged form.
Suitable elements E
1
and E
2
in the chelating ligands (R
1
)(R
2
)E
1
—A′—Z(R
5
)—B′—E
2
(R
3
)(R
4
) (II) of the metal complexes (I) of the invention are the elements of main group V of the periodic table of the elements (group VA), i.e. nitrogen, phosphorus, arsenic, antimony or bismuth. Particularly suitable elements are nitrogen or phosphorus, especially phosphorus. The chelating ligands in (II) can contain different elements E
1
and E
2
; for example, it is possible for E
1
to be nitrogen and for E
2
to be phosphorus.
The bridging structural unit in the metal complexes of the invention is composed of the components A′, B′ and Z (see also formulae (I) and (II)). For the purposes of the present invention, the bridging structural unit is basically a multiatomic group which connects the elements E
1
and E
2
to one another.
The component Z used is either nitrogen or phosphorus, especially nitrogen.
The units A′ and B′ can be, in each case independently of one another, C
1
-C
4
organocarbon or organosilicon radicals. Suitable organic radicals are C
1
-C
4
-alkylene units in substituted or unsubstituted form, for example methylene, ethylene, propylene, and also ethylidene, propylidene and benzylidene. Preference is given to using methylene, ethylene, ethylidene and benzylidene, particularly preferably methylene.
Furthermore, A′ and B′, likewise independently of one another, can be silylene radicals, for example —R
a
—Si—R
b
—, where R
a
, R
b
are C
1
-C
4
-alkylene units in substituted or unsubstituted form, for example methylene, ethylene or ethylidene, arylene units, in particular o-phenylene, or aralkylidene units, in particular benzylidene, where the free valencies on the silicon may be saturated by alkyl groups such as methyl, isopropyl or t-butyl, aryl groups such as phenyl, or aralkyl groups such as benzyl.
A′ and B′ can also each be an —NR
6
unit wher
Queisser Joachim
Schäfer Ansgar
Schulz Michael
Slany Michael
Acquah Samuel A.
BASF - Aktiengesellschaft
Keil & Weinkauf
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