Abstract
The mechanism of the uranyl ion photoinitiated polymerization of acrylamide has been studied in aqueous solutions and in acetone. Steady-state and dynamic luminescence quenching studies show that initiation proceeds through a thermally activated bimolecular interaction between *UO22+ and monomer involving electron or charge transfer. Results from various studies show that the mechanism previously suggested for this process, involving energy transfer, is incorrect. ESR studies suggest that initiation involves formation of a uranium(V)-radical pair. Polymerization then proceeds through a radical mechanism in both solvents. With the exception of the chloride, the yields do not depend upon the counter-ion. Polymer is frequently produced with adsorbed uranyl ions, which can be separated by dialysis. In agreement with previous studies, photopolymerization proceeds without significant overall reduction in the uranyl concentration. It is shown that this is probably due to any intermediate uranium(V) being reoxidized by monomer, with concurrent thermal initiation of polymerization.
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