Abstract
Radical copolymerization of propiolaldehyde (MB) with styrene (MA) was carried out at 60°C over a wide range of monomer feed compositions. It was shown from the results of IR, NMR, and UV spectral analyses of the copolymers that propiolaldehyde was copolymerized through the acetylenic opening to give the conjugated enal unit, , and that the copolymerization had a rather high tendency to alternation. The behavior is also in agreement with the results predicted by the statistically calculated parameters such as dyad fraction, average sequence length, and run number. Monomer reactivity ratios (rA=0.32 and rB=0.21) and the Q and e values (Q=0.83 and e=0.84) are compared with those of some acetylenic monomers and the corresponding vinyl monomers. Propiolaldehyde is found to show the highest polymerization reactivity among the acetylenic monomers. This may be due to the activation of the acetylenic group by conjugation with the electron-withdrawing aldehyde group.
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K. Kobayashi and H. Sumitomo, J. Polym. Sci., Part B, 10, 703 (1972).
K. W. Doak, J. Am. Chem. Soc., 72, 4681 (1950).
C. C. Price and C. E. Greene, J. Polym. Sci., 6, 111 (1951).
H. Higashiura, Kogyo Kagaku Zasshi (J. Chem. Soc. Japan, Chem. Ind. Sect.), 69, 1243 (1966).
S. Takahashi, K. Takemoto, and M. Imoto, Kobunshi Kagaku (Chem. High Polymers), 26, 374 (1969).
J. C. Sauer, Org. Syn., 36, 66 (1956).
K. Ito and Y. Yamashita, J. Polym. Sci., Part A, 3, 2165 (1965).
K. Meyersen, R. C. Schulz, and W. Kern, Makromol. Chem., 58, 204 (1962).
F. A. Bovey and G. V. D. Tiers, Fortschr. Hochpolym. Forsch., 3, 139 (1963).
A. E. Gillam and E. S. Stern, “An Introduction to Electronic Absorption Spectroscopy in Organic Chemistry” 2nd ed, Edward Arnord Publishers Ltd., London, 1957, p 70.
E. R. Blout and M. Fields, J. Am. Chem. Soc., 70, 189 (1948).
T. Ouchi and M. Oiwa, Kogyo Kagaku Zasshi (J. Chem. Soc. Japan, Ind. Chem. Sect.), 72, 1587 (1969).
I. Takemura and H. Sumitomo, Abstracts, SPSJ 18th Symposium, Tokyo, Nov., 1969, p 39.
L. J. Young and C. C. Kennedy in “Copolymerization,” G. E. Ham, Ed., John Wiley & Sons, Inc., New York, N. Y., 1964, p 845.
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Kobayashi, K., Sumitomo, H. Polymerization of Propiolaldehyde. II. Radical Copolymerization of Propiolaldehyde with Styrene. Polym J 4, 194–199 (1973). https://doi.org/10.1295/polymj.4.194
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DOI: https://doi.org/10.1295/polymj.4.194