Catalyst mixture and polymerizable composition

Details Catalyst mixture and polymerizable composition Catalyst mixture and polymerizable composition

1998-09-30

2000-12-19

Teskin, Fred

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526281, 526283, 526308, 526309, 502152, 502155, 25218214, 25218215, 25218217, 25218218, 428403, 428404, 428426, 428457, 428689, 428698, C08G 6108, C08G 6112

Patent

active

061628832

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a mixture consisting of at least one thermal ruthenium catalyst A and at least one ruthenium carbene catalyst B, both of which initiate the ring-opening metathesis polymerisation on their own, said catalysts being present in a weight ratio of A to B from 10:1 to 1:10; to a composition consisting of at least one strained cycloolefin and a catalytically effective amount of the ruthenium catalyst mixture; to a process for the polymerisation of strained cycloolefins; to shaped articles of polymers of said composition and to the use of the ruthenium catalyst mixture for the ring-opening metathesis polymerisation of strained cycloolefins.
The ring-opening metathesis polymerisation of strained cycloolefins such as norbornene with catalysts selected from the ruthenium compound group is known and has been repeatedly described in the literature.
A. Demonceau et al. in J. Mol. Catal. 76:123-132 (1992), for example, describe ruthenium compounds as suitable metathesis polymerisation catalysts of e.g. norbornene, where the reactivity can be increased by the addition of diazo esters.
In Tetrahedron Letters 52:4589-4592 (1977), C. Tanelian et al. report that the ruthenium compound RuCl.sub.2 [P(C.sub.6 H.sub.5).sub.3 ].sub.3 is a suitable catalyst for the metathesis polymerisation but that it is deactivated by dicyclopentadiene and then no polymers are formed.
WO 93/20111 proposes the use of ruthenium compounds with phosphine ligands, for example [(H.sub.5 C.sub.6).sub.3 P].sub.2 Cl.sub.2 Ru.dbd.CH--CH.dbd.C(C.sub.6 H.sub.5).sub.2, as thermal catalysts for the ring-op thesis polymerisation of strained cycloolefins, where cyclodienes such as dicyclopentadiene act as catalyst inhibitors and therefore cannot be polymerised. These "metal carbenes" are sparingly soluble compounds, so that the polymerisations are only possible in polar and, where appropriate, protic solutions. The same catalysts are described by S. Kanaoka in Macromolecules 1995, 28, pages 4707 to 4713 under the same conditions of solution polymerisation for the preparation of copolymers with silicon-containing norbornene derivatives.
In Polym. Prepr. 1995, 36, pages 237 to 238, C. Fraser et al. describe ruthenium carbenes having a Ru.dbd.CH--C.sub.6 H.sub.5 group which are effective catalysts for the metathesis polymerisation. A substantial disadvantage of these catalysts is their high reactivity which makes it necessary to process polymerisable compositions directly after the components are mixed.
WO 95/07310 describes a ring-opening photopolymerisation of strained cycloolefins under the action of ruthenium compounds with photolabile ligands as catalysts. After being irradiated, these catalysts can also be used as thermal catalysts.
Carbene-free ruthenium catalysts normally must be used in amounts of more than 0.3% by weight, and ruthenium carbene catalysts normally must be used in amounts of more than 0.1% by weight, based on the cycloolefin, in order to obtain, within reasonable polymerisation times, well polymerised shaped artices having good mechanical and physical properties. If lower amounts are used, the polymerisation is not complete anymore which can be detected by the inherent smell of the monomers used and their bad physical and mechanical properties. It is not possible to prepare useful shaped articles using such low amounts.
The ruthenium catalysts are expensive and their use in higher amounts as catalysts is uneconomical. Another disadvantage is that the use of high amounts of catalysts also leads to high amounts of ruthenium residues in the polymers, which is undesirable for toxic reasons, adversely affects the stability of the polymer and must be avoided in particular where there is contact with electrical or electronic components.
Surprisingly, it has now been found that the high reactivity of the ruthenium carbene catalysts can be reduced, a latency of polymerisable compositions can be achieved and, within a specific scope, even the reactivity can be adjusted, which obviates immediate processing owing to the

REFERENCES:
patent: 5266665 (1993-11-01), Hardiman
patent: 5849851 (1998-12-01), Grubbs et al.
Demonceau et al, J. Molecular Catalysis, vol. 76, pp. 123-132 (1992).
Kanaoka et al, Macromolecules, vol. 28, pp. 4707-4713 (1995).
Tanelian et al, Tetrahedron Letters, vol. 52, pp. 4589-4592 (1977).

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