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The Mechanism and Kinetics of the Heterogeneous Polymerization of Vinyl Monomers. II. The Benzoyl Peroxide Catalyzed Polymerization of Vinylidene Chloride

W. I. Bengough and R. G. W. Norrish
Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences
Vol. 218, No. 1133 (Jun. 25, 1953), pp. 149-154
Published by: Royal Society
Stable URL: http://www.jstor.org/stable/99306
Page Count: 6
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Since scans are not currently available to screen readers, please contact JSTOR User Support for access. We'll provide a PDF copy for your screen reader.
The Mechanism and Kinetics of the Heterogeneous Polymerization of Vinyl Monomers. II. The Benzoyl Peroxide Catalyzed Polymerization of Vinylidene Chloride
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Abstract

The polymerization of vinylidene chloride initiated with from 0· 02 to 1· 0 mol.% benzoyl peroxide has been studied at temperatures from 47 to 75° C. In all cases the rate of polymerization was found to increase throughout the first 30% polymerization. The reaction rate when compared at equal extents of conversion was found to vary as the square root of the benzoyl peroxide concentration. In the presence of tetrahydrofuran the rate of polymerization remained constant during the early stages of the reaction. These results can be explained by the mechanism put forward in part I, namely, that active centres undergo transfer reactions with 'dead' polymer resulting in the formation of immobile polymer centres which continue to grow and are finally terminated by chain transfer reactions with monomer.

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