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Encyclopedia of Physical Science and Technology EN001F-4 May 7, 2001 16:19

88 Acetylene

reactions and derivatives of Vinylox are shown in ions), while acetylenic nitriles give new 1,3-thiazine sys-
Fig. 14. tems and polyconjugated iminodihydrofurans. Figure 15
New epoxy resins of unique structures and high purity summarizes some of this novel chemistry, some deriva-
which are nontoxic, noncorrosive, and possess lower than tives of which exhibit pesticide and other bioactivity.
expected viscosities are readily formed from this versatile
monomer. The cured epoxy resin, in turn, exhibits higher
strengthandgreaterflexibilityinavarietyofcompositeap- SEE ALSO THE FOLLOWING ARTICLES
plications. Polyols, glycols, carbohydrates, dicarboxylic
and hydroxycarboxylic acids, polythiols, and other sulfur CATALYSIS,INDUSTRIAL • PHARMACEUTICALS • PHY-
hydroxy compounds react readily with Vinylox to form SICAL ORGANIC CHEMISTRY
the corresponding polyglycidyl derivatives. Vinylox and
its derived epoxides are used as adhesives, active diluents,
plasticizers, and modifiers for diverse epoxide materials. BIBLIOGRAPHY
Small additions of Vinylox to synthetic rubbers enhance
their strength, elasticity, and water-freeze resistance. This
Bilow, N., Landis, A. L., and Boschan, R. H. (1978). U.S. Patents
monomer and some of its derivatives exert a thermostabi-
4,098,767 and 4,100,138.
lizing effect on PVC formulations. Vinylox can be copoly- Bilow, N., Landis, A. L., and Boschan, R.H. (1982). SAMPE J.
merized with both radical initiators and anionic catalysts Brandsma, L., Vasilevsky, S. F., and Verkruijsse, H. D. (1997). “Appli-
to give curable copolymers with n-butylvinyl ether, vinyl cation of Transition Metal Catalysts in Organic Synthesis,” Springer-
acetate, N-vinylpyrrolidone, and other typical monomers. Verlag, Berlin/New York.
Copenhaver, J. W., and Bigelow, M. H. (1949). “Acetylene and Carbon
With cationic catalysts, Vinylox forms both soluble and
Monoxide Chemistry,” pp. 246–294, Reinhold, New York.
cross-linked polymers, depending on conditions. Kirk, R. E., and Othmer, D. F. (1978). “Encyclopedia of Chemical Tech-
Potentially important derivatives of Vinylox are nology,” 3rd ed., Vol. 1, pp. 192–276, Wiley-Interscience, New York.
2-vinyloxyethoxy-methyl thirane (trade name Vinylox-S) McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1977).
and 3-(2-vinyloxyethoxy)-propylene-1,2-carbonate (trade J. Chem. Soc., Chem. Commun. p. 578.
McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1978).
name Cyclovin).
Appl. Phys. Lett. 33, 180.
McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1978).
J. Am. Chem. Soc. 100, 1013.
F. Hydroxyacetylenic Esters and Nitriles McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1979).
Coat. Plast. Prepr. Pap. Meet. Am. Chem. Soc., Div. Org. Coat. Plast.
Trofimov and co-workers have explored the chemistry of
Chem.
γ -hydroxy-α,β-acetylenic esters and acetylenic nitriles, McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1979–
prepared by the following routes. 1980). Synth. Met. 1, 101–118.
McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1982).
Phys. Rev. B: Condens. Matter [3] 26, 2327–2330.
1. CuCl 2 McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1984).
R 2 C C CH + CO + MeOH−−−→
| PdCl 2 Mol. Cryst. Liq. Cryst. 105, 89–107.
OH McDiarmid, A. G., Park, Y. W., Heeger, A. J., and Shirakawa, H. (1984).
R 2 C C C CO 2 Me Polym. Prepr. Am. Chem. Soc., Div. Polym. Chem.
| Miller, S. A. (1965–1966). “Acetylene, Its Properties, Manufacture and
OH Uses,” Vols. 1, 2, Academic Press, New York.
KOBr Pasedach, H., Dimroth, P., and Schneider, K. (1961). German Patent
2. R 2 C C CH−−−→ 1,098,953.
OH Pasedach, H., Dimroth, P., and Schneider, K. (1962). German Patents
1,129,941 and 1,130,803.
CuCN
R 2 C C C Br −−−→ R 2 C C C CN Pasedach, H., Dimroth, P., and Schneider, K. (1963). German Patents
DMSO 1,135,894 and 1,145,632.
OH OH Pasedach, H., Dimroth, P., and Schneider, K. (1963). U.S. Patent
3,082,216.
Roth, S. (1995). “One-Dimensional Metals,” VCH, Weinbeim/New
Esters and nitriles derived from tertiary acetylenic al- York.
cohols add smoothly to diverse O-, N-, and S-containing Salaneck, W. R., Lundstr¨om, I., and Ranby, B., eds. (1993). “Nobel Sym-
❡
nucleophilestoyieldhetrovinylderivativeswhichundergo posium in Chemistry: Conjugated Polymers and Related Materials:
intramolecular cyclization to dihydrofurans and other het- The Interconnection of Chemical and Electrical Structure,” Oxford
Scientific, Oxford.
erocycles. From this chemistry, novel spirocyclicimines,
Selwitz, C. M., and Sabourn, E. T. (1978). U.S. Patents 4,128,588.
lactones, and 1,3-oxathiolanes have been obtained from Selwitz, C. M., and Sabourn, E. T. (1980). U.S. Patents 4,204,078,
sulfur containing nucleophiles (sulfide and rhodanide 4,215,226, 4,216,341, 4,219,679, and 4,223,172.