Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1997-05-14
1999-10-26
Lewis, Michael
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526280, 526281, 585 22, 585361, C08F 480, C07C 1361
Patent
active
059730854
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to compounds having at least two strained cycloolefins bonded directly or via a bridging group; compositions comprising these compounds and a one-component catalyst for thermally induced and/or radiation-induced metathesis polymerization; a polymerization process, crosslinked polymers from the compounds mentioned and, if appropriate, other olefins and/or cycloolefins suitable for metathesis polymerization; carrier materials coated with these crosslinked polymers; and a polymerization process.
WO 93/13171 describes air- and water-stable one-component and two-component catalysts based on molybdenum compounds and tungsten compounds containing carbonyl groups and ruthenium compounds and osmium compounds with at least one polyene ligand for the thermal metathesis polymerization and a photoactivated metathesis polymerization of strained cycloolefins, in particular norbornene and norbornene derivatives. No other polycyclic--above all non-fused polycyclic cycloolefins are mentioned. The one-component catalysts of the ruthenium compounds used, that is to say [(C.sub.6 H.sub.6) Ru(CH.sub.3 CN).sub.2 Cl].sup.+ PF.sub.6.sup.- and [Ru(cumene)Cl.sub.2 ].sub.2, can indeed be activated by UV irradiation; however, the storage stability of the compositions with norbornene are [sic] completely inadequate. These catalysts are capable of replacing the known two-component catalysts only inadequately.
Demonceau et al. [Demonceau, A., Noels A. F., Saive, E., Hubert, A. J., J. Mol. Catal. 76:123-132(1992)] describe (C.sub.6 H.sub.5).sub.3 ].sub.3 PRuCl.sub.2 [sic], (p-cumene)RuCl.sub.2 P(C.sub.6 H.sub.11).sub.3 and (C.sub.6 H.sub.5).sub.3 ].sub.3 PRuHCl [sic] as thermal catalysts for ring-opening metathesis polymerization of norbornene, a fused polycycloolefin. These catalysts have not found acceptance in industrial preparation because their activity is too low. It is therefore proposed to increase the activity by the addition of diazo esters. It is also mentioned that only (p-cumene)RuCl.sub.2 P(C.sub.6 H.sub.11).sub.3 is capable of polymerizing norbornene in a relatively short time at 60.degree. C. Cyclooctene is also mentioned as a further monomer. No other cycloolefins for methatesis [sic] polymerization are mentioned.
Petasis and Fu [Petasis, N. A., Fu, D., J. Am. Chem. Soc. 115:7208-7214 (1993)] describe thermal ring-opening metathesis polymerization of norbornene using biscyclopentadienyl-bis(trimethylsilyl)methyl-titanium(IV) as a thermally active catalyst. No other cycloolefins for metathesis polymerization are mentioned. EP 287,762 describes crosslinked copolymers of a mixture of 1,2-bisnorbornenyl-ethane of the formula ##STR1## and a compound of the fromula [sic] ##STR2## which are prepared using catalyst systems for thermal metathesis polymerization comprising a catalyst and an activator. A disadvantage of these systems is the need to separate the catalyst and activator, so that no storage-stable polymerizable compositions can be provided. The catalyst and activator can be combined only directly before the polymerization, highly reactive compositions which rapidly gel with evolution of heat being formed. The production of shaped articles is therefore limited to certain processes, such as, for example, the RIM process. The resulting crosslinked polymers have high softening temperatures. No coated materials are mentioned.
It has now been found that compositions of compounds comprising at least two strained cycloolefins bonded directly or via a bridge group and a one-component catalyst are storage-stable and have an outstanding processability, even in the presence of oxygen and moisture, depending on the choice of catalyst. These compositions can be processed by means of the most diverse shaping processes to give crosslinked metathesis polymers without special safety precautions. The polymers have high crosslinking densities and outstanding mechanical and electrical properties as well as surface properties, for example low .epsilon. values and tan .delta. values, and a very low absorption of
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Hafner Andreas
Muhlebach Andreas
Van Der Schaaf Paul Adriaan
Ciba Specialty Chemicals Corporation
Crichton David R.
Ghyka Alexander G.
Hall Luther A. R.
Lewis Michael
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