Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Patent
1996-05-16
1998-05-19
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 63, 522 66, 522168, 522172, 522188, 522186, 522184, 526104, 526281, 526283, C08F 250, C08F 422, C08F 3204, C08F 3400
Patent
active
057537216
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for the polymerisation of cyclic olefins by photochemical ring-opening metathesis polymerisation using catalytic amounts of a transition metal catalyst, and to compositions comprising said olefins together with a catalytic amount of said catalyst.
Thermally induced ring-opening metathesis polymerisation using catalytic amounts of metal catalysts has been known for some considerable time and is widely described in the literature (q.v. inter alia K. J. Ivin, Olefin Metathesis, Academic Press, London, 1983). Such polymers are prepared industrially and are commercially available. However, photochemically induced ring-opening metathesis polymerisation is only little known and so far commercial utilities have not resulted.
U.S. Pat. No. 4 060 468 discloses an olefin metathesis polymerisation which is carried out by charging a two-component mixture of a metal salt selected from tungsten, molybdenum, rhenium and tantalium salts and a substituted phenol or benzyl alcohol as co-catalysts to a reactor with the olefin monomer, and then irradiating the entire reaction mixture with UV light The only olefins mentioned are cyclic and acylic hydrocarbons without functional groups or substituents. The separate storage of the catalyst components and the process step of mixing the catalyst components directly before the actual reaction make the known process technically complicated and troublesome.
In Tetrahedron Letters No. 52, pp. 4589-4592 (1977), C. Tanielan et al. describe the catalyst system W(CO).sub.6 /CCl.sub.4, which, after irradiation with UV light, can be used for the metathesis polymerisation of cyclopentene and norbornene. Metal carbonyls are volatile and toxic, so that their use requires elaborate protective measures for physiological reasons. In addition, a free radical addition reaction is observed as competing reaction to form monomeric 1-chloro-2-trichlormethylcycloolefins.
It is known from H. H. Thoi et al., Journal of Molecular Catalysis, 15 (1982), pp. 245-270, that a tungsten pentacarbonylcarbene complex of formula ##STR1## is a thermal catalyst for the ring-opening metathesis polymerisation of dimethyl norbornene and, together with phenyl acetylene as co-catalyst, is also a photocatalyst system for the same polymerisation. This catalyst system has the serious shortcoming that, as ready-for-use formulation, it has only poor storage stability, the carbonyl compound is physiologically unacceptable, and the tolerance to functional groups in cycloolefins is too low.
J. Feldmann et al describe in Progress in Inorganic Chemistry, Vol. 39, pp. 3-73, Edited by Stephen J. Lippard (1991), molybdenum and tungsten alkylidene complexes which, singly, are only poor, but together with Lewis acids, are effective, thermal catalysts for the polymerisation of cycloolefins.
In WO 93/13171 are described one component catalysts on the basis of carbonyl containing Mo- and W-compounds and Ru- or Os-compounds with a polyene ligand for the ring-opening photometathesis of strained cycloolefines. With this catalysts are obtained storage stable compositions under exclusion of light.
N. A. Petasis et al. mention in J. Am. Chem. Soc. 115 (1993), pages 7208-7214 the thermal ring-opening photometathesis of norbornene in using thermal catalysts. A photoinitiating activity is not mentioned.
The known catalysts which can be activated photochemically thus mainly require a co-catalyst, for which reason the quality of the resultant polymers can vary greatly owing to the chosen nature and sequence of the reactants.
Polymers obtained from cyclic olefins by photochemical ring-opening metathesis polymerisation can only be prepared by the known processes with a great deal of trouble and in an economically unsatisfactory manner. Particular disadvantages are the poor stability, which only permits the components to be mixed directly before the preparation, the lack of tolerance to functionalised cyclic olefins, and the necessity of using two components as catalyst system. Hence for technical, economic and e
REFERENCES:
patent: 4060468 (1977-11-01), Castner
J. Amer. Chem Soc. vol. 107 pp. 6739-6740 (1985) S. J. Landon et al.
Journal of the Chem Soc. p. 187 (1975) A. Agapiou et al.
Tetrahedron Letters vol. 34 No. 38 pp. 6123-6126 B. Gita et al. (1993).
W. Feast et al. J. Mol. Catal. 65: 63-72 (1991).
J. Feldman et al "Advances in Alkylidenes", Progress in Inorganic Chemistry pp. 1-74 (1991).
F. Huq et al. J. Chem. Soc. Comm. 1079-1080 (1971).
K. Ivin et al. Olefin Metathesis 1-12 Academic Press (1983).
R. Schrock et al. J. Am. Chem. Soc. 112:3875-3886 (1990).
C. Tanielan et al. Tetrahedron Letters 52: 4589-4592 (1977).
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S. Trofimenko, Chem. Rev. 93: 943-980 (1993).
Hafner Andreas
Muhlebach Andreas
van der Schaaf Paul A.
Berman Susan W.
Ciba Specialty Chemicals Corporation
Malia Victoria M.
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