Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1997-06-16
2000-07-25
Wu, David W.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526161, 526164, 526169, 526170, 526172, 526281, 526283, C08F 3802
Patent
active
060937793
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to compositions comprising nonvolatile acetylenes and photocatalytic amounts of a molybdenum, tungsten, niobium or tantalum catalyst which either comprises at least two methyl groups or two monosubstituted methyl groups without .alpha. hydrogen atoms in the substituent, or comprises at least one halogen and only one silylmethyl group attached to the metal; to a photopolymerization process for preparing polyacetylenes; to a two-stage process for photopolymerization and subsequent thermal polymerization of nonvolatile acetylenes; to carrier materials having at least one layer comprising nonvolatile acetylenes together with a catalytic amount of this catalyst; and to carrier materials having at least one layer of nonvolatile polyacetylenes or having a relief structure comprising polyacetylenes.
Voronkov et al. [Voronkov, M. G., Pukhnarevich, V. B., Sushchinskaya, S. P., Annenkova, V. Z., Annenkova, V. M., Andreeva, N. J., J. Polymer Science: Polymer Chemistry Edition 18:53-57 (1980)] describe the polymerization of acetylene and substituted acetylenes using molybdenum halides and tungsten halides in 1,2-dichloroethane. Masuda et al. [Masuda, T., Okano, Y., Kuwane, Y., Higashimura, T., Polymer Journal 12:907-913 (1980)] describe the same reaction in other halogenated solvents or in hydrocarbons. The catalysts are so reactive that formation of polymer takes place at room temperature or even at lower temperatures. Consequently, the compositions are difficult to process and, accordingly, have not acquired any importance whatsoever.
Masuda et al. [Masuda, T., Kawasaki, M., Okano, Y., Higashimura, T., Polymer Journal 14:371-377 (1982)] mention that, using cocatalysts such as, for example, tetraphenyltin or triethylaluminum, it is possible to increase the reactivity of molybdenum halides and tungsten halides in the polymerization of acetylenes. A description is also given of how molybdenum hexacarbonyl and tungsten hexacarbonyl, following irradiation with UV light for one hour in the presence of CCl.sub.4, form an active catalyst system for the polymerization of acetylenes.
Tamura et al. [Tamura, K., Masuda, T., Higashimura, T., Polymer Bulletin 32:289-296 (1994)] describe how molybdenum hexacarbonyl and tungsten hexacarbonyl together with Lewis acids, following irradiation with UV light, are effective initiators for the polymerization of acetylenes.
Gita and Sundarajan [Gita, B., Sundarajan, G., Tetrahedron Letters 34:6123-6126 (1993)] describe the preparation of block copolymers by metathesis polymerization of norbornene and phenylacetylene using UV-irradiated W(CO).sub.6 /CCl.sub.4. The preparation of static polymers of norbornene and phenylacetylene was described earlier by Masuda et al. [Masuda, T., Yoshida, T., Makio, H., Rahman, M.Z.A., Higashimura, T., J. Chem. Soc., Chem. Commun. 503-504 (1991)].
Nothing has to date been disclosed in the art regarding the direct photopolymerization of substituted or unsubstituted acetylenes alone or together with strained cycloolefins.
It has now surprisingly been found that nonvolatile acetylenes, alone or together with certain one-component catalysts, constitute compositions which are storage stable if light and moisture are excluded and which, under the action of actinic radiation, are subject to a metathesis polymerization or copolymerization, the polymers being formed in short reaction times and with good to very good yields. It has also been found that it is sufficient, surprisingly, to initiate the polymerization by irradiation and then to continue it under the action of heat, it has also been surprisingly found that the polymerization can be carried out without solvent, a fact which opens up wider possibilities for application, an example being the direct preparation of moldings by bulk polymerization.
One subject of the invention is a composition comprising at least one nonvolatile acetylene alone or together with a stained cycloolefin and catalytic amounts of a catalyst for metathesis polymerization, which comprises at least one one-co
REFERENCES:
patent: 4667006 (1987-05-01), Ai et al.
patent: 5753721 (1998-05-01), Hafner et al.
patent: 5776997 (1998-07-01), Hafner et al.
Derwent Abst. 86-187072 (1986).
Masuda et al, Journal Chem. Soc., Chemical Communications, Apr. 1991, pp. 503-504.
Tetrahedron Letters, vol. 34, No. 38, Sep. 1993, pp. 6123-6126.
Hafner Andreas
Muhlebach Andreas
Van Der Schaaf Paul Adriaan
Ciba Specialty Chemicals Corporation
Hall Luther A. R.
Lu-Rutt Caixia
Wu David W.
LandOfFree
Polymerizable acetylene composition and acetylene photopolymeriz does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Polymerizable acetylene composition and acetylene photopolymeriz, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Polymerizable acetylene composition and acetylene photopolymeriz will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-1337186