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Ionic Polymerization. IX. The Effect of Water in the Cationic Polymerization of Styrene Catalyzed by Stannic Chloride

Overberger, C. G. and Ehrig, R. J. and Marcus, R. A. (1958) Ionic Polymerization. IX. The Effect of Water in the Cationic Polymerization of Styrene Catalyzed by Stannic Chloride. Journal of the American Chemical Society, 80 (10). pp. 2456-2463. ISSN 0002-7863. doi:10.1021/ja01543a028.

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This work was undertaken in order to obtain information on the mechanistic role of water on the polymerization of styrene catalyzed by stannic chloride. The polymerization and molecular weight were studied as a function of the concentration of water and of the other reagents in a nitrobenzene-carbon tetrachloride solvent medium at 25°. Unusually stringent drying conditions and a quantitative measure of water permitted the water content in these experiments to be known with high accuracy and allowed data to be obtained not available from previous work. A high vacuum technique was employed for introduction of all reagents, and the polymerization rate was following dilatometrically The initial rate of the reaction was observed to increase to a maximum and then decrease as the initial concentration of water was increased. The decrease in rate has been attributed partly to heterogeneity. At a constant initial water concentration, the reaction was found to be first order with respect to the stannic chloride concentration between 0.005 and 0.02 M, and approximately second order with respect to the monomer concentration between 1 and 3 M. The degree of polymerization of the resulting polymer increases with the initial monomer concentration, decreases with the water concentration, and is essentially independent of the catalyst concentration. A reaction mechanism has been proposed to account for these results, in which a monohydrate catalyst-cocatalyst complex is assumed. Termination is postulated to occur by a spontaneous unimolecular process and a bimolecular process involving water. A monomer transfer step is also indicated.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1958 American Chemical Society. Received June 10, 1957. The authors gratefully acknowledge the support of part of this work by the Office of Naval Research, Contract No. Nonr 343 (00), Project NR356-262. The authors are also greatly indebted to Professor F. S. Dainton for permission to see his papers on the polymerization of styrene in advance of publication and during the preparation of this paper. This is the ninth in a series of papers concerned with ionic polymerization. For the eighth paper, see C. G. Overberger. E. M. Pearce and D. Tanner, THIS JOURNAL, 80, 1761 (1955). From the dissertation submitted by R. J. Ehrig to the Graduate School of the Polytechnic Institute of Brooklyn in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
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Office of Naval Research (ONR)Nonr 343 (00)
Issue or Number:10
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Official Citation:Ionic Polymerization. IX. The Effect of Water in the Cationic Polymerization of Styrene Catalyzed by Stannic Chloride C. G. Overberger, R. J. Ehrig, and R. A. Marcus Journal of the American Chemical Society 1958 80 (10), 2456-2463 DOI: 10.1021/ja01543a028
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59463
Deposited By: George Porter
Deposited On:13 Aug 2015 02:15
Last Modified:10 Nov 2021 22:21

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