Process for the polymerization of cyclic olefins and polymerizab

Details Process for the polymerization of cyclic olefins and polymerizab Process for the polymerization of cyclic olefins and polymerizab

1996-03-08

1998-12-29

Berman, Susan W.

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

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

522 29, 522 65, 522170, 522179, 522184, 522185, 522188, 526171, 526252, 526268, 526280, C08F 248, C08F 442, C08F 3200, C08F13200

Patent

active

058542990

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a process for the polymerization of cyclic olefins by photochemical ring-opening metathesis polymerization using catalytic amounts of a transition metal catalyst, and to compositions comprising these olefins together with a catalytic amount of this catalyst.
Thermally induced ring-opening metathesis polymerization using catalytic amounts of metal catalysts has already been known for a relatively long time and has been described in several instances in the literature (cf., for example, K. J. Ivin, Olefin Metathesis, Academic Press, London, 1983). Such thermal polymers are prepared industrially and are commercially obtainable.
On the other hand, only little has been disclosed on photochemically induced ring-opening metathesis polymerization, and as yet there have been no commercial applications. It is furthermore known from this publication that olefin metathesis reactions can be initiated photochemically by WCl.sub.6 catalysts. However, this type of catalyst is extremely sensitive to oxygen and moisture, which makes its storage and use considerably more difficult. Furthermore, these catalysts can be employed only within a relatively narrow temperature range, since they tend to decompose at elevated temperature.
It is known from U.S. Pat. No. 4,060,468 to carry out an olefin metathesis polymerization by introducing a two-component mixture of a metal salt chosen from the group consisting of tungsten, molybdenum, rhenium and tantalum salts and a substituted phenol or benzyl alcohol as cocatalysts to a reaction vessel with the monomeric olefin, and then irradiating the entire reaction mixture with UV light. Olefins which are mentioned are only cyclic and acyclic hydrocarbons without functional groups or substituents. Separate storage of the catalyst components and the process step of mixing the catalyst components directly before the actual reaction render the known process industrially expensive and cumbersome.
C. Tanielan et al. describe, in Tetrahedron Letters No. 52, pages 4589 to 4592 (1977), the catalyst system W(CO).sub.6 /CCl.sub.4, which, after irradiation with UV light, can be employed for metathesis polymerization of cyclopentene and norbornene. Metal carbonyls are volatile and toxic, so that their use requires expensive safety precautions for physiological reasons.
Furthermore, a free radical addition reaction to form monomeric 1-chloro-2-trichloromethyl-cycloolefins is observed as a competing reaction.
It is known from H. H. Thoi et al., Journal of Molecular Catalysis, 15 (1982), pages 245 to 270 that a tungsten pentacarbonyl-carbene complex of the formula ##STR1## is a thermal catalyst for ring-opening metathesis polymerization of dimethylnorbornene, and, together with phenylacetylene as a cocatalyst, is also a photocatalyst system for the same polymerization. This catalyst system has the serious disadvantage that it has only a low storage stability as the ready-to-use formulation, the carbonyl compound is physiologically unacceptable, and the tolerance towards functional groups in cycloolefins is too low.
The known photochemically activatable catalysts thus always require a cocatalyst, which means that the quality of the polymers prepared can vary greatly due to the chosen nature and sequence of the reagents.
Polymers can be prepared from cyclic olefins by photochemical ring-opening metathesis polymerization by the known processes only with high expenditure and in an economically unsatisfactory manner. The lack of storage stability, which allows mixing of the components only directly before the preparation, the lack of tolerance towards functionalized cyclic olefins and the need to use two components as the catalyst system have been found to be particular disadvantages. There is therefore a need to provide a process, which is improved from the industrial, economic and ecological aspect and is generally usable, for the preparation of polymers from cyclic olefins by photochemical ring-opening metathesis polymerization.
It has been found that compositions of cycloole

REFERENCES:
patent: 4060468 (1977-11-01), Castner
patent: 5089536 (1992-02-01), Palzzotto
"Ullmann's Encyclopedia of Industrial Chemistry", 5.sup.th Edition, vol. B4, pp. 12-14.
M. A. Bennet et al., J.C.S. Dalten Trans., 233-241 (1974).
M.A. Bennet et al. J. Organomet. Chem. 175:87-93 (1979).
W. Feast et al. J. Mol. Catal. 65:63-72 (1991).
W.R. Gilkerson et al. J. Am. Chem. Soc. 101:4096-411 (1979).
S. J. Landen et al. J. Am.Chem Soc. vol. 107:6739-6740 (1985).
S. Luo et al. J. Am. Chem. Soc. 114:8515-8520 (1992).
C. Tanielan et al. Tetrahedran letters No. 52:pp. 4589-4592 (1977).
H.H. Thoi et al. J.Mel.Catal. 15:245-270 (1982).
Ivin, K.S, Oletin Methathesis, Academic Press, pp. 1-13, London (1983).

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