Abstract
AbstractMethyl methacrylate was polymerized in a homogeneous organic medium composed of a solvent of high dielectric constant an ionizable salt and the monomer. Application of a direct current provided a controlled initiation of the polymerization process by the discharged ionic species. The influence of the type of solvent electrode material and salt on the yield and molecular weight of polymer was assessed in preliminary experiments. Polymers of high molecular weight were obtained in contrast to low degrees of polymerization reported in earlier work. The yield of polymer was linearly dependent on the time, and kinetic analysis showed that the rate of reaction was proportional to the current density. The molecular weight showed an inverse dependence on current density. A rate scheme is proposed which provides a kinetic interpretation of the experimental results on the basis of a free radical mechanism initiated by the electrolytic discharge of acetate ions. The electrical control of the physical properties of the resultant polymer by programming of the current‐time dependence is discussed.
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