Electrochemical polymerization to a controlled molecular weight distribution

Living polyanions were generated by the passage of electrolytic current through solutions in tetrahydrofuran (THF). The concentration of living polyanions was controlled by the current and could be increased by further electrolysis or decreased by electrolysis with reversal of polarity. Inasmuch as the living end (LE) concentration determines the molecular weight at a given monomer concentration it was possible to program a molecular weight distribution. Model distributions were attempted by (1) indirect methods in which an electrolytic formation of initiating dianions was followed by monomer addition, polymerization, current reversal and further polymerization and (2) direct methods in which monomer was present throughout the electrolysis. The molecular weight distributions were obtained by gel-permeation chromatography and corresponded closely to the values calculated from the simple kinetic model of anionic polymerization. For styrene a sharp low molecular weight fraction and a clear binodal high molecular weight fraction were obtained. The binodal character was attributed to the growth of active single-ended and double-ended polyanions. The yields of high and low molecular weight material, the ratios of molecular weights obtained, and the values of the molecular weights were in agreement with expectation. The direct electrochemical polymerization methods were employed for α-methylstyrene, but the high k_p for styrene thwarted efforts to apply the direct technique with this monomer.