Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-12-30
2001-05-15
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...
C526S281000, C526S161000, C526S943000, C502S152000
Reexamination Certificate
active
06232413
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to the use of &pgr; systems or of metallocene compounds in which a transition metal with two &pgr; systems, and in particular with aromatic &pgr; systems, such as anionic cyclopentadienyl ligands (carbanions) is complexed and the two systems are bonded reversibly to one another by at least one bridge of a donor and an acceptor, as organometallic catalysts in a process for the preparation of cycloolefin (co)polymers for use for optical data memories, by (co)polymerization of monomers from the group consisting of cyclic olefins, &agr;-olefins having 2 or more C atoms and optionally conjugated for non-conjugated diolefins. The coordinate bond formed between the donor atom and the acceptor atom produces a positive (part) charge in the donor group and a negative (part) charge in the acceptor group:
BACKGROUND OF THE INVENTION
Cycloolefin (co)polymers are distinguished by many advantageous properties, for example by a high transparency for use for their application in the field of optical data memories, in particular for compact disks (CDs) of high memory density. They furthermore have a good heat resistance, resistance to aging, resistance to chemicals, resistance to solvents, low absorption of water, high scratch resistance, low birefringence of light and high softening points (glass transition temperatures T
g
).
Metallocenes 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 furthermore known from EP-A '368 that metallocenes in combination with aluminum-alkyl/water as cocatalysts are active systems for the polymerization of ethylene (thus, for example, methylaluminoxane=MAO is formed from 1 mol of trimethylaluminum and 1 mol of water. Other stoichiometric ratios have also already been used successfully (WO 94/20506)). Metallocenes in which the cyclopentadienyl skeletons are linked to one another covalently via a bridge are also already known. An example of the numerous Patents and Applications in this field which may be mentioned is EP-A 704 461, 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. The bridged metallocenes are also envisaged as polymerization catalysts for olefins in EP '461. In spite of the numerous Patents and Applications in this field, there continues to be a demand for improved catalysts which are distinguished by a high activity, so that the amount of catalyst remaining in the polymer can be set to a low level, and which are equally suitable for the (co)polymerization of cycloolefins, for the preparation of which metallocenes have likewise already been employed (U.S. Pat. No. 5,567,777; EP 610 852=U.S. Pat. No. 5,602,219; EP 690 078).
SUMMARY OF THE INVENTION
It has now been found that particularly advantageous catalysts can be prepared from bridged &pgr; complex compounds, and in particular from metallocene compounds, in which the bridging of the two &pgr; systems is established by one, two or three reversible donor-acceptor bonds, in which in each case a coordinate or so-called dative bond which is overlapped at least formally by an ionic bond forms between the donor atom and the acceptor atom, and in which one of the donor or acceptor atoms can be part of the particular associated &pgr; system. The reversibility of the donor-acceptor bond also allows, in addition to the bridged state identified by the arrow between D and A, the non-bridged state. &pgr; systems according to the invention which are to be employed, for example metallocenes, can therefore be described by a double arrow and the formula part (Ia) and (Ib) or (XIIIa) and (XIIIb) to include both steps.
DETAILED DESCRIPTION OF THE INVENTION
The invention accordingly relates to a process for the preparation of cycloolefin (co)polymers for use for optical data memories, by (co)polymerization of monomers from the group consisting of cyclic olefins, &agr;-olefins having 2 or more C atoms and optionally conjugated or non-conjugated diolefins in the gas, bulk, solution or slurry phase at −78 to +200° C. under 0.5-70 bar in the presence of organometallic catalysts which can be activated by cocatalysts, which comprises employing as the organometallic catalysts metallocene compounds of the formula
in which
CpI and CpII are two identical or different carbanions having a cyclopentadienyl-containing structure, in which one to all of the H atoms can be replaced by identical or different radicals from the group consisting of linear or branched C
1
-C
20
-alkyl, which can be monosubstituted to completely substituted by halogen, mono- to trisubstituted by phenyl or mono- to trisubstituted by vinyl, C
6
-C
12
-aryl, halogenoaryl having 6 to 12 C atoms, organometallic substituents, such as silyl, trimethylsilyl or ferrocenyl, and 1 or 2 can be replaced by D and A,
D denotes a donor atom, which can additionally carry substituents and has at least one free electron pair in its particular bond state,
A denotes an acceptor atom, which can additionally carry substituents and has an electron pair gap in its particular bond state,
where D and A are linked by a reversible coordinate bond such that the donor group assumes a positive (part) charge and the acceptor group assumes a negative (part) charge,
M represents a transition metal of sub-group III, IV, V or VI of the Periodic Table of the elements (Mendeleev), including the lanthanides and actinides,
X denotes an anion equivalent and
n denotes the number zero, one, two, three or four, depending on the charge of M,
or &pgr; complex compounds, and in particular metallocene compounds of the formula
in which
&pgr;I and &pgr;II represent different charged or electrically neutral &pgr; systems which can be fused to one or two unsaturated or saturated five- or six-membered rings,
D denotes a donor atom, which is a substituent of &pgr;I or part of the &pgr; system of &pgr;I and has at least one free electron pair in its particular bond state,
A denotes an acceptor atom, which is a substituent of &pgr;II or part of the &pgr; system of &pgr;II and has an electron pair gap in its particular bond state,
where D and A are linked by a reversible coordinate bond such that the donor group assumes a positive (part) charge and the acceptor group assumes a negative (part) charge, and where at least one of D and A is part of the particular associated &pgr; system,
where D and A in turn can carry substituents,
where each &pgr; system and each fused-on ring system can contain one or more D or A or D and A and
where in &pgr;I and &pgr;II in the non-fused or in the fused form, one to all of the H atoms of the &pgr; system independently of one another can be replaced by identical or different radicals from the group consisting of linear or branched C
1
-C
20
-alkyl, which can be monosubstituted to completely substituted by halogen, mono- to trisubstituted by phenyl or mono- to trisubstituted by vinyl, C
6
-C
12
-aryl, halogenoaryl having 6 to 12 C atoms, organometallic substituents, such as silyl, trimethylsilyl or ferrocenyl, or one or two can be replaced by D and A, so that the reversible coordinate D→A bond is formed (i) between D and A, which are both parts of the particular &pgr; system or the fused-on ring system, or (ii) of which D or A is (are) part of the &pgr; system or of the fused-on ring system and in each case the other is (are) a substituent of the non-fused n system or the fused-on ring system,
M and X have the above meaning and
n denotes the number zero, one, two, three or four depending on the charges of M and those of &pgr;-I and &pgr;-II.
&pgr; systems according to the invention are substituted and unsubstituted ethylene, allyl, pentadienyl, benzyl, butadiene, benzene, the cyclopentadienyl anion and the species which result by replacement of at least one C atom by a heteroatom. Among the species mentioned, the cyclic species are
Kelly Warren Mark
Schmid Claudia
Starzewski Karl-Heinz Aleksander Ostojola
Stumpf Andreas
Bayer Aktiengesellschaft
Cheung Noland J.
Gil Joseph C.
Harlan R.
Wu David W.
LandOfFree
Method for producing cycloolefin (CO) polymers for use in... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method for producing cycloolefin (CO) polymers for use in..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for producing cycloolefin (CO) polymers for use in... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2549014