Advances in Catalysis, Vol. 2 by W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

By W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

With this moment quantity of Advances in Catalysis, the editors have persevered their efforts to provide the numerous features of the catalytic procedure. a few hugely certified males have contributed to this quantity. From the theoretical remedies of user-friendly approaches among molecules reacting at reliable surfaces to the technically very important activities of fluoride catalysts, and to catalytic polymerizations of olefins, the reader turns into conversant in manifold rules and with a few regular experimental effects in relation to catalytic phenomena. Our loss of a whole realizing of catalytic motion, and our corresponding lack of ability to ''predict'' the way of accomplishing a wanted catalytic response, make it necessary for everybody operating during this path to familiarize himself with the adventure of others, whether such event used to be amassed in distant sectors of this mammoth box.

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Carbonium Ion Mechanism The most widely accepted mechanism (Whitmore, 13) for the polymerization of olefins involves the so-called carbonium ions. I n accordance with this mechanism a carbonium ion (usually a tertiary ion) adds to the olefin to form a higher molecular weight carbonium ion which then yields the olefin polymer by elimination of, usually, a proton. , sulfuric acid) the initial carbonium ion is formed by addition of the hydrogen ion from the acid to the extra electron pair in the double bond (the pi electrons): 28 LOUIS SCHMERLINQ AND V.

None of the products which would be formed by the addition of the sec-butyl carbonium ion to the Zbutene or t o isobutylene were obtained. The rate of addition of the sec-butyl ion to the olefinic double bond is apparently too slow; this finds analogy in the comparative ease of addition of tert-butyl chloride and sec-butyl chloride to ethylene in THE MECHANISM OF THE POLYMERIZATION OF ALKENES 47 the presence of Friedel-Crafts type catalysts (Schmerling, 46). 1-Butene is not formed as an intermediate because loss of a proton occurs more readily from the methylene group than from the methyl group.

I. INTRODUCTION I . Scope The chemical literature contains 'very many papers on the polymerization of olefins, written both from the theoretical and practical standpoint. A discussion of the large variety of olefins, catalysts and conditions which have been investigated is beyond the scope of this article. Thomas, 6). It is the primary purpose of this chapter to discuss the mechanism of the reaction, and particularly those mechanisms which have been proposed during the past fifteen years.

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