Abstract
In the polymerization of isobutyi vinyl ether, Et2AlCl was inactive by itself and highly activated by oxygen. A limited amount of oxygen contacted with Et2AlCl at −78°C gave a stereoregular polymer in a good yield. The catalytically active species was stable only at low temperatures. Iodometrical titration and low temperature IR spectroscopy indicated that the concentration of the active species was proportional to that of the peroxide, e.g., EtAl(OOEt)Cl, a thermally unstable intermediate formed in the course of oxidation of Et2AlCl by oxygen. EtAl(OOCMe2Ph)Cl catalyses the process in a similar fashion to that of the “low temperature Et2AlCl–O2catalyst system.” The oxidation of Et2AlCl and the catalytic activity of the products are studied. The effects of carbon dioxide are reasonably interpreted in terms of the competitive coordination between oxygen and carbon dioxide toward organo-aluminums.
Similar content being viewed by others
Article PDF
References
O. Yamamoto, Bull. Chem. Soc. Jpn., 35, 619 (1962).
G. Natta, G. Dall’Asta, G. Mazzanti, U. Giannini, and S. Cesca, Angew. Chem., 71, 205 (1959).
G. Natta, M. Peraldo, M. Farina, and G. Bressan, Makromol. Chem., 55, 139 (1962).
K. Matsuzaki, M. Hamada, and K. Arita, J. Polym. Sci., Part A-1, 5, 1233 (1967).
G. A. Razuvajev and A. J. Grajevskii, Dokl. Akad. Nauk SSSR, 128, 309 (1959).
N. Ueyama, T. Araki, and H. Tani, unpublished result.
E. G. Hoffmann, Z. Elektrochem., 64, 616 (1960).
K. Mach, Collect. Czech. Chem. Commun., 28, 2295 (1963).
R. Tarao and S. Takeda, Bull. Chem. Soc. Jpn., 40, 650 (1967).
J. P. Kennedy, Polym. Prepr., 7, 485 (1966).
H. Hirata and H. Tani, Polymer, 9, 59 (1968).
W. P. White, J. Phys. Chem., 24, 393 (1920).
H. Scherer and G. Seydel, Angew. Chem., 75, 846 (1963).
A. G. Davies, “Organic Peroxides,” Butterworths Scientific Publns., London, 1961.
H. Hock, H. Kropf, and F. Ernst, Angew. Chem., 71, 541 (1959).
K. Ziegler, “Organoaluminum Compounds,” ACS Monograph, No. 147, Zeiss Ed., Reinhold, New York, N. Y., 1960.
S. Takahashi, K. Sonogashira, and N. Hagihara, Nippon Kagaku Zasshi (J. Chem. Soc. Japan, Pure Chem. Sect.), 87, 610 (1966).
L. Vaska, Science, 140, 809 (1963).
N. L. Zutty and F. J. Welch, J. Org. Chem., 25, 861 (1960).
A. G. Davies, D. G. Hare, and O. R. Kahn, J. Chem. Soc., 1125 (1963).
M. H. Abraham and A. G. Davies, J. Chem. Soc., 429 (1959).
A. G. Davies and C. D. Hall, J. Chem. Soc., 1192 (1963).
J. M. Bruce and D. W. Farren, Polymer, 4, 407 (1963).
T. Higashimura, T. Yonezawa, S. Okamura, and K. Fujii, J. Polym. Sci., 39, 487 (1959).
S. Okamura, T. Higashimura, and H. Yamamoto, J. Polym. Sci., 33, 510 (1958).
S. Okamura, T. Higashimura, and I. Sakurada, J. Polym. Sci., 39, 507 (1959).
T. Higashimura, K. Suzuoki, and S. Okamura, Makromol. Chem., 86, 259 (1965).
D. J. Cram and K. R. Kopecky, J. Am. Chem. Soc., 81, 2748 (1959).
M. Goodman and Y. L. Fan, J. Am. Chem. Soc., 86, 4922 (1964).
C. E. H. Bawn and A. Ledwith, Quart. Revs., 16, 361 (1962).
E. J. Vandenberg, R. F. Heck, and D. S. Breslow, J. Polym. Sci., 41, 519 (1959).
H. Hirata, Ph. D. Thesis, Osaka University, 1969.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Hirata, H., Araki, T. & Tani, H. Polymerization of Isobutyi Vinyl Ether by Diethylaluminum Chloride. Requirement of Cocatalyst. Polym J 4, 279–289 (1973). https://doi.org/10.1295/polymj.4.279
Issue Date:
DOI: https://doi.org/10.1295/polymj.4.279