Thermal metathesis polymerization process and a polymerisable co

Details Thermal metathesis polymerization process and a polymerisable co Thermal metathesis polymerization process and a polymerisable co

1997-05-14

1999-12-28

Zitomer, Fred

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526260, 526172, 526280, 526281, 526283, 526309, C08F 480

Patent

active

060083069

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a process for the thermal polymerization of strained cycloolefins; a thermally polymerizable composition of such a cycloolefin and a one-component catalyst for thermally induced metathesis polymerization; and carrier materials coated with the thermally polymerizable or the crosslinked polymers.
Demonceau et al. [Demonceau, A., Noels, A. F., Saive, E., Hubert, A. J., J. Mol. Catal. 76:123-132 (1992)] describes [(C.sub.6 H.sub.5).sub.3 P].sub.3 RuCl.sub.2, (p-cymene)RuCl.sub.2 P(C.sub.6 H.sub.11).sub.3 and [(C.sub.6 H.sub.5).sub.3 P].sub.3 RuHCl as thermal catalysts for ring-opening metathesis polymerization of norbornene, a fused polycycloolefin. Because the activity is too low, these catalysts have not found acceptance in industrial preparation. It has therefore been suggested that the activity be increased by the addition of diazo esters. It is also mentioned that only (p-cymene) 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.
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 polycyclical--above all non-fused polycyclical--cycloolefins are mentioned. The one-component catalysts of the ruthenium compounds used, that is to say [Ru(cumene)Cl.sub.2 ].sub.2 and [(C.sub.6 H.sub.6)Ru(CH.sub.3 CN).sub.2 Cl].sup.+ PF.sub.6 --, can indeed be activated by UV irradiation; however, the storage stability of the compositions with norbornene is completely inadequate. These catalysts are capable of replacing the known two-component catalysts only inadequately.
It has now been found, surprisingly, that divalent-cationic ruthenium and osmium complexes are highly active one-component catalysts for thermally induced metathesis polymerization if they contain at least one phosphine group with bulky substituents bound to the metal atom. It has furthermore been found that the compositions are stable to air and moisture and can be processed without safety precautions. The polymerizable compositions comprising ruthenium and osmium complexes are moreover sufficiently stable, so that they do not polymerize before the desired type of processing.
The invention relates to a composition of (a) at least one strained cycloolefin and (b) a catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium, wherein the ruthenium or osmium compound contains a metal atom to which are bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with the proviso that in ruthenium (trisphenylphosphine)dihalides or hydride-halides the phenyl groups are substituted by C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 haloalkyl or C.sub.1 -C.sub.18 alkoxy.
The cyclical olefins can be monocyclical or polycyclical condensed or bridged ring systems, having for example from two to four rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si in one or more rings and/or can contain condensed aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclical rings can contain 3 to 16, preferably 3 to 12 and, particularly preferably, 3 to 8 ring members. The cyclical olefins can include further nonaromatic double bonds, depending on the ring size preferably 2 to 4 such additional double bonds. The ring substituents are those which are inert, in other words which do not adversely affect the chemical stability of the ruthenium compounds and osmium compounds. The cycloolefins are strained r

REFERENCES:
Mueting et al., Inorg. Synth. (1992) 29, 279-98.
Yoshida et al., Polym J. (Tokyo) (1998) 30 (10), 819-823.
Demonceau et al, Journal of Molecular Catalysis, vol. 76, (1992), pp. 123-132.

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