Determination of kinetic rate constants in electrochemically initiated anionic polymerization of 1,3‐butadiene

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Abstract
The rate constants for electrochemically initiated polymerization were determined by employing a pulsing technique. An electrochemical titration was conducted in which polymer chains were initiated electrochemically, propagated in the absence of current, and terminated electrochemically. The concentrations of supporting electrolyte and monomer were chosen to correspond to those employed in electropolymerization syntheses. The temperature range −10°C to −72°C gave kp = 1.45 × 102 exp {2600/RT}. The Arrhenius parameters are compared to those from previous studies and are interpreted in terms of ion‐pair propagation. Precise control of molecular weight distributions is implicit from an accurate knowledge of the kinetic parameters and is reported separately.