Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-03-18
2003-12-02
Lu, Caixia (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C556S007000, C556S013000, C556S027000, C556S052000, C556S053000, C502S103000, C502S152000, C502S155000, C526S133000, C526S134000, C526S351000, C526S943000
Reexamination Certificate
active
06657027
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 bonded together by at least one bridge containing a donor and an acceptor, at least one substituent on the acceptor group being a fluorinated aryl radical, to the use of these compounds as catalysts and to a process for the polymerization of olefins.
BACKGROUND OF THE INVENTION
The coordinate bond existing between the donor atom and the acceptor atom produces a (partial) positive charge in the donor group and a (partial) negative charge in the acceptor group:
The invention further relates to the use of these 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). It is also known from EP-A-129 368 that metallocenes, in combination with alkylaluminum/water as co-catalysts, are effective systems for the polymerization of ethylene, (thus, for example, methylaluminoxane=MAO is formed from approx. 1 mol of trimethylaluminum and 1 mol of water). Other stoichiometric proportions have also already been used successfully (WO 94/20506)). Metallocenes whose cyclopentadienyl skeletons are covalently linked together by a bridge are also already known. EP-A-704 461 may be cited as an example of the numerous patents and patent applications in this field, the linking group mentioned in said patent being a (substituted) methylene group or ethylene group, a silylene group, a substituted silylene group, a substituted germylene group or a substituted phosphine group. EP-A-704 461 also provides the bridged metallocenes as polymerization catalysts for olefins.
Catalysts with a donor-acceptor interaction and their use as polymerization catalysts are known in principle.
Thus, WO-A-98/01455 describes compounds in which a transition metal is complexed with two &pgr; systems, especially with aromatic &pgr; systems (metallocenes), and the two systems are reversibly bonded together by at least one bridge containing a donor and an acceptor, the donor or acceptor atoms being bonded as substituents on the &pgr; systems; it also describes their use as polymerization catalysts.
WO-A-98/45339 describes compounds in which a transition metal is complexed with two &pgr; systems, especially with aromatic &pgr; systems (metallocenes), and the two systems are reversibly bonded together by at least one bridge containing a donor and an acceptor, at least one of the donor or acceptor atoms being part of the respective &pgr; system; it also describes their use as polymerization catalysts.
Patent applications WO-A-98/01483 to WO-A-98/01487 describe industrial polymerization processes which use the described catalysts with a donor-acceptor interaction.
It is known from said documents that the catalysts with a donor-acceptor interaction can advantageously be used as catalysts for the polymerization of olefins.
However, it was a surprise to those skilled in the art that particularly advantageous catalysts with a donor-acceptor interaction could be prepared by selecting special substitution patterns on the acceptor group.
SUMMARY OF THE INVENTION
Therefore, the present invention provides transition metal compounds with two &pgr; systems and at least one donor-acceptor interaction between these &pgr; systems, characterized in that these transition metal compounds have at least one fluorine-substituted aryl group on at least one acceptor atom.
DETAILED DESCRIPTION OF THE INVENTION
&pgr; systems according to the present invention are substituted and unsubstituted ethylene, allyl, pentadienyl, benzyl, butadiene, benzene, the cyclopentadienyl anion and species produced by replacing at least one C atom with a heteroatom, said species preferably being cyclic. The coordination of such ligands (&pgr; systems) to the metal can be of the &sgr; type or of the &pgr; type.
Suitable transition metal compounds with at least one donor-acceptor interaction are the transition metal compounds with a donor-acceptor interaction described in patent applications WO-A-98/01455, WO-A-98/45339 and WO-A-98/01483 to WO-A-98/01487, characterized in that these transition metal compounds have fluorine-substituted aryl groups on the acceptor group.
Particularly suitable compounds are the metallocenes of the formula
in which
CpI and CpII are two identical or different carbanions with a cyclopentadienyl-containing structure, in which one to all of the H atoms can be substituted by identical or different radicals from the group comprising linear or branched C
1
-C
20
-alkyl which can be monosubstituted to fully substituted by halogen, monosubstituted to trisubstituted by phenyl and monosubstituted to trisubstituted by vinyl, C
6
-C
12
-aryl, halogenoaryl having 6 to 12 C atoms, and organometallic substituents such as silyl, trimethylsilyl and ferrocenyl, and can be monosubstituted or disubstituted by D and A,
D is a donor atom which can additionally carry substituents and which, in its respective bonding state, has at least one free electron pair,
A is an acceptor atom which carries at least one fluorine-substituted aryl group, but preferably exclusively fluorine-substituted aryl groups, as substituents and which, in its respective bonding state, has an electron pair deficiency,
D and A being linked by a reversible coordinate bond in such a way that the donor group assumes a (partial) positive charge and the acceptor group a (partial) negative charge,
M is a metal of groups III-VII of the periodic table of the elements as defined by IUPAC (1985), including the lanthanides and actinides,
X is one anion equivalent and
n is the number zero, one, two, three or four, depending on the charge of M.
The first and second carbanions CpI and CpII with a cyclopentadienyl skeleton can be identical or different. The cyclopentadienyl skeleton can for example be one of the group of cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene, wherein fluorene and substituted fluorene are preferred. There may be 1 to 4 substituents per cyclopentadiene ring or fused benzene ring. These substituents can be C
1
-C
20
-alkyl such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl or eicosyl, C
1
-C
20
-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy or eicosyloxy, halogens 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 or xylyl, halogenophenyl such as fluoro-, chloro- or bromophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, pentachlorophenyl, naphthyl or biphenylyl, triorganylsilyl such as trimethylsilyl (TMS), ferrocenyl, and D or A, as defined above. Fused aromatic rings can also be partially or completely hydrogenated, leaving only the double bond to which both the fused ring and the cyclopentadiene ring contribute. Furthermore, benzene rings, as in indene or fluorene, can carry one or two additional fused benzene rings. Also, the cyclopentadiene or cyclopentadienyl ring and a fused benzene ring can together carry an additional fused benzene ring. In the form of their anions, such cyclopentadiene skeletons are excellent ligands for transition metals, each cyclopentadienyl carbanion of said optionally substituted form compensating one positive charge of the central metal in the complex.
Specific examples of such carbanions are cyclopentadienyl, methylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, indenyl, phenylindenyl, 1,2-diethylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, n-octylcyclopentadienyl, &bgr;-phenylpropylcyclopentadienyl, tetrahydroindenyl, propylcyclopentadienyl, t-butylcyclopentadien
Ostoja-Starzewski Karl-Heinz Aleksander
Xin Bruce S.
Bayer Aktiengesellschaft
Cheung Noland J.
Gil Joseph C.
Lu Caixia
Seng Jennifer R.
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