Abstract
Addition of propylene oxide to phenol with lithium phenoxide as a catalyst was studied under various temperature as well as composition conditions. The kinetic study of this reaction rules out an ionic mechanism and proposes instead a multi-centred reaction in which the three component associated transition complex rearranges to yield reaction products. Arrhenius parameters in the case of lithium phenoxide exhibit marked deviations from those of homologue alkali phenoxides: there is an abrupt and unusually high decrease in the activation energy accompanied by a corresponding decrease in the frequency factor, the reaction velocity remaining almost unchanged. This compensation effect takes place as a result of a multi-centred reaction in homogeneous phase.
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R. E. Parker and N. S. Isaacs, Chem. Rev., 59, 737 (1959).
J. Furukawa and T. Saegusa, “Polymerization of Aldehydes and Oxides”, Polymer Reviews, Part 3, Interscience Publishers, New York N.Y., 1963.
C. C. Price, “The Polyethers”, Chapter 11; R. J. Gritter, “Reactions of Cyclic Ethers”, Chapter 9.
E. Staude and F. Patat, “Cleavage of the C–O–C-Bond”, Chapter 2 in “The Chemistry of the Ether Linkage”, S. Patai Ed., Interscience Publishers, London, 1967.
T. G. Pritchard and F. A. Long, J. Am. Chem. Soc., 78, 2667 (1956).
T. G. Pritchard and F. A. Long, J. Am. Chem. Soc., 78, 6008 (1956).
J. D. Worsfold and E. M. Eastham, J. Am. Chem. Soc., 79, 897 (1957).
G. T. Merrall, G. A. Latremouille, and E. M. Eastham, Can. J. Chem., 38, 1967 (1960).
C. K. Ingold, “Structure and Mechanism in Organic Chemistry”, Cornell University Press, Ithaca, N.Y., 1953.
W. Weibull and B. Nylander, Acta Chim. Scand., 8, 847 (1954).
F. Patat, Kuststoffe Plast., 5, 297 (1958).
F. Patat and B. Wojtech, Makromol. Chem., 37, 1 (1960).
F. Patat and E. Wittmann, Z. Naturforsch., Ser. 1, 18, 169 (1963).
S. Sakai and Y. Ishii, Kogyo Kagaku Zasshi (J. Chem. Soc. Japan, Industrial Chem. Sect.), 61, 358 (1958).
S. Sakai and Y. Ishii, Kogyo Kagaku Zasshi, 61, 1473 (1958).
S. Sakai and Y. Ishii, Kogyo Kagaku Zasshi, 62, 413 (1959).
See also an article by Ishii and Sakai in “Ring-Opening Polymerization”, K. C. Frisch and S. L. Reegen, Ed., Marcel Dekker, New York, N.Y., 1969, p 20.
J. Furukawa and T. Saegusa in “Polymer Reviews”, Vol. 3, Interscience Publishers, New York, N. Y., 1963, p 141.
D. R. Boyd and E. Marie, J. Chem. Soc., 105, 2117 (1914).
H. Tiltscher and E. Staude, Angew. Makromol. Chem., 10, 97 (1970).
J. Itakura and F. Patat, Makromol. Chem., 68, 158 (1963).
D. J. Worsfold and S. Bywater, Can. J. Chem., 38, 1801 (1960).
H. Sinn and O. T. Onsager, Makromol. Chem., 55, 167 (1962).
E. Wittmann, Ber. Bunsenges. Phys. Chem., 67, 817 (1963).
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Staude, E., Hussain, A. The Lithium Phenoxide Catalyzed Addition of Propylene Oxide to Phenol. Polym J 2, 468–474 (1971). https://doi.org/10.1295/polymj.2.468
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DOI: https://doi.org/10.1295/polymj.2.468