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It is generally admitted that the Smith‐Ewart equation is not applicable to the emulsion polymerization of vinyl acetate. This is considered to be due to two factors, namely, (1) the great solubility in water of vinyl acetate and (2) the fact that vinyl acetate is easily subject to the influences of retarders or chain transfer agents. However, examination of the polymerization of vinyl caproate and of styrene leads to the conclusion that the special features pertaining to the polymerization of vinyl acetate are to be attributed to its solubility in water. The reason is that vinyl caproate, which is less soluble in water but subject to the influences of retarders or chain transfer agents in the same degree as vinyl acetate, follows the Smith‐Ewart equation in emulsion polymerization, and styrene, when polymerized in aqueous methanol, in which the solubility of styrene increases, shows a diminished Smith‐Ewart exponent.
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Okamura et al. (1962) studied this question.
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