Macromolecules

Determination of Rate Constants in the Carbocationic Polymerization of Styrene: Effect of Temperature, Solvent Polarity, and Lewis Acid 1

P De, R Faust, H Schimmel, AR Ofial, H Mayr

Index: De, Priyadarsi; Faust, Rudolf; Schimmel, Holger; Ofial, Armin R.; Mayr, Herbert Macromolecules, 2004 , vol. 37, # 12 p. 4422 - 4433

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Citation Number: 38

Abstract

The electrophilicity parameter (E= 9.6) of the 1-phenylethyl cation, 1+, has been determined and combined with the nucleophilicity parameter (N= 0.78, s= 0.95) of styrene (St) to predict diffusion-limited propagation in the cationic polymerization of St by the linear free energy relationship log k= s (N+ E). This prediction has been experimentally verified using two different diffusion clock methods, which provided a value of kp±≈ 2× 109 L mol-1 s-1, 6 ...