Absolute propagation rates in emulsion polymerization I. Butadiene in mutual system

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Abstract
A study has been carried out on the emulsion polymerization of butadiene, using the Mutual Recipe, in an attempt to evaluate the absolute propagation rate, according to the theory of Smith and Ewart, from a determination of the rate of polymerization per particle of latex. It was found, as expected, that the number of particles formed is a function of the temperature of initiation, almost doubling in number for a 10°C. rise in temperature. This number is also a function of the soap charge, being approximately proportional to the square root of the soap concentration. Unlike the case of styrene polymerization, the rate of polymerization per particle was found to be affected by the amount of soap adsorbed on the particle, hence it cannot be considered as representing the true propagation rate for butadiene. However, the rate of polymerization, when calculated per mole of soap present, was found to be a function of temperature only, yielding an activation energy value of ca. 14 kcal.

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